Tinted lenses and methods of manufacture

ABSTRACT

The present invention recognizes that lenses, such as contact lenses, can be pigmented using ink that include polymers or polymerizable monomers, preferably the same monomers used to make the lens. Preferably, such lenses are made using bonding agents. The ink can be used to make images on or within the lens. Images made using these inks are preferably digital and can be used in a variety of printing methods, including ink-jet printing.

The present application is a Continuation-in-Part of U.S. patentapplication Ser. No. 10/128,064 to Doshi, entitled “Tinted lenses andmethods of manufacture”, filed on 23 Apr. 2002; which is aContinuation-in-Part of U.S. patent application Ser. No. 09/949,520, toDoshi filed Sep. 7, 2001 now U.S. Pat. No. 6,834,955; which is adivisional of U.S. patent application Ser. No. 09/969,933, to Doshi,filed Oct. 25, 2000, now U.S. Pat. No. 6,315,410; which claims benefitof priority to U.S. provisional patent application Ser. No. 60/218,710,to Doshi, filed Jul. 17, 2000; and claims benefit of priority to U.S.provisional patent application No. 60/162,695, to Doshi filed Nov. 1,1999; and claims benefit of priority to PCT application PCT/US00/41454,published as WO 01/40846, to Doshi, filed Oct. 23, 2000; each of whichis incorporated herein by reference.

TECHNICAL FIELD

The present invention generally relates generally to the fields oftinted lenses and methods of manufacture.

BACKGROUND

Tinted contact lenses have steadily gained in popularity since theirintroduction into the marketplace. In particular, colored contact lensesthat include images that mimic the iris of an eye are particularlypopular. However, colored contact lenses made by traditionaltechnologies suffer from poor image quality and other difficulties,including leaching of pigments present on the surface of lenses,unnatural appearances, fading of colors and limited number of colors tochoose from. The present invention addresses these problems, andprovides additional and related benefits as well.

A variety of colored contact lenses and methods of making them have beendescribed. For example, U.S. Pat. No. 5,018,849 to Su et al., issued May28, 1991, describes colored contact lenses that form a laminatedstructure whereby a pigment is provided on the top layer of the contactlens and opaque material is sandwiched between two layers of the contactlens material, such as polymers. The opaque material blocks the naturalcolor of the wearer's iris, and the pigment gives the wearer's eye theappearance of a desired color. These contact lenses have the undesirablequality of looking unnatural due to the limited number of colors thatare available. In addition, during manufacture the opaque material andpigment are applied to the contact lens material in a plurality ofsteps, using one color per step.

In U.S. Pat. No. 5,034,166 to Rawlings et al., issued Jul. 23, 1991,non-laminated colored contact lenses are described. The pigment in thistype of colored contact lens is casted into the structure of the lensmaterial. The pigment is dispensed one color at a time during lensmanufacturing which limits the number of colors that can be used to makecolored contact lenses. The resulting colored contact lens isundesirable because the wearer's eyes appear unnatural. Furthermore, thepattern and pigments used in this method is limited which results in anunnatural looking contact lens. Also, existing methods provide customerswith limited choices of colors and patters and the lenses produced bythese methods can provide pigments on the a surface of a lens, which canmake the lenses uncomfortable for the wearer and prone to fading of thepigment.

The colored contact lenses described in U.S. Pat. No. 5,106,182 toBriggs et al., issued Apr. 21, 1992, described a laminated coloredcontact lens. In this contact lens, pigmentation is provided on oneportion of a contact lens using a pad transfer method using a rubberstamp having raised radial segments. The pad transfer method appliespigment to the portion of the contact lens to form a crude pattern. Thepad is then pressed to the portion of the contact lens to smear thepigment and the pad disengaged from the portion of a contact lens. Thelens is rotated, and the process is repeated as desired. The resultingcolored contact lens is undesirable because of the limited number ofcolors that can be used and the resulting pigmentation pattern has anunpredictable and unnatural appearance.

U.S. Pat. No. 5,160,463 to Evans et al., issued Nov. 3, 1992, describesa colored contact lens made by applying a first pigment in a firstpattern to a molding device. Additional pigments in additional patternscan be applied to the molding device in independent applications. Theresulting image on the molding device can be transferred to a contactlens. The use of multiple printing steps is undesirable due to theincreased number of applications that are needed to create an image. Inaddition, this method results in an image of unnatural appearance due tothe limited number of colors that can be used to create the image.

Colored contact lenses reported in U.S. Pat. No. 5,414,477 to Jahnke,issued May 9, 1995, relate to images that are made using pad transfermethods to form a plurality of dots of unnatural appearance. A pluralityof printing processed can be used to create an image comprising morethan one color that reportedly results in an image with a more naturalappearance. These dots are of relatively definite in shape andrelatively large in size and thus have an unnatural appearance. Thecolored contact lenses made using these methods also have a limitednumber of colors and patterns that can be used, which results in anunnatural looking product.

The present invention addresses the problems associated with describedtinted contact lenses by providing an image on or within a contact lensthat is of superior quality. The increased quality of the image resultsin a tinted contact lens that has a natural appearance.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 depicts a schematic diagram of a method of printing digitallyencoded images. A1 denotes black ink; A2 denotes magenta ink; A3 denotesyellow ink; A4 denotes cyan ink; A6 denotes color ink coat/layer ofA1+A2+A3+A4. The digitally encoded image is printed on a surface such asa lens.

FIG. 2 depicts diagram of laminate digitally encoded images encasedwithin a structure. A6 denotes color ink coat/layer of black, magenta,yellow and cyan; A7 denotes partially polymerized monomer mix for clearlens; A8 denotes partially polymerized A6; A9 denotes fully polymerizedclear lens.

FIG. 3A depicts a method of encasing a layer of ink between a primarysurface and a polymer layer. A5 denotes a monomer mix for clear lens; A6denotes color ink coat/layer of black, magenta, yellow and cyan; A7denotes partially polymerized A5; A8 denotes partially polymerized A6;A9 denotes fully polymerized clear lens; A10 denotes fully polymerizedA6.

FIG. 3B depicts a method of applying ink to a surface.

FIG. 4 depicts a diagram of pad transfer printing method of the presentinvention. A7 denotes partially polymerized monomer mix for clear lens;A8 denotes partially polymerized color ink coat/layer of black, magenta,yellow and cyan; A9 denotes fully polymerized clear lens. A10 denotes afully polymerized A8.

FIG. 5 depicts a method of a lathe/fabrication process that can be usedto produce lens of the present invention.

FIG. 6 depicts cast molded method that can be used to produce lens ofthe present invention.

FIG. 7A and FIG. 7B depict spin cast methods that can be used to producelens of the present invention.

FIG. 8A depicts examples of indentation structures that can be formed onthe convex portion of the present invention and are depicted as filledwith an ink of the present invention.

FIG. 8B depicts examples of indentation structures that can be formed onthe concave portion of the present invention and are depicted as filledwith an ink of the present invention. The indentation structures are notnecessarily shown to scale and preferably are relatively small such thatthey have a volume of less than about 10 microliters, less than about 5microliters, less than about 1 microliter, less than about 0.1microliter, less than about 1 nanoliter, less than about 0.1 nanoliteror less than about 0.01 nanoliters.

FIG. 9 depicts deposition of ink into a variety of indentationstructures of the present invention. Different angles represent rotationof surface. The indentation structures are represented as beingpartially filled with an ink of the present invention. The remainingvoid volume in the indentation structures can be filled with, forexample, a monomer or a polymer such as to trap the ink of the presentinvention. Droplets of one or more colors of ink can be deposited intosuch indentations to allow for a variety of colors to be present in suchindentations.

FIG. 10 depicts a fixture for centering and masking for lenses,preferably but not limited to hydrated or partially hydrated lenses.

FIG. 11 depicts schematic diagram of a variety of methods for printingdigitally encoded images in conjunction with the present invention.

FIG. 12 depicts schematic diagrams of a variety of methods of makingpolymers having printed digitally encoded images. A5 denotes a monomermix for clear lens.

FIG. 13 depicts diagram of laminate digitally encoded images within astructure of the present invention. A5 denotes a monomer mix for clearlens; A6 denotes color ink coat/layer of black, magenta, yellow andcyan; A7 denotes partially polymerized A5; A8 denotes partiallypolymerized A6; A9 denotes fully polymerized clear lens; A10 denotesfully polymerized A6.

FIG. 14 depicts printing methods within a well on a surface of thepresent invention. A5 denotes a monomer mix for clear lens; A6 denotescolor ink coat/layer of black, magenta, yellow and cyan; A7 denotespartially polymerized A5; A8 denotes partially polymerized A6; A9denotes fully polymerized clear lens.

SUMMARY

The present invention recognizes that lenses, such as contact lenses,can be tinted using ink that includes polymers or polymerizablemonomers, preferably the same monomers used to make the lens. The inkcan be used to make images on or within the lens. Images made usingthese inks are preferably in a modified or unmodified digital format andcan be used in a variety of printing methods, including ink-jetprinting. Modified digital formats can be made by altering the digitalimage before or after printing such as by vibration applied to theprinted surface.

A first aspect of the present invention is an article of manufacture,including: a polymer and a digitally encoded image made with ink,wherein the polymer forms a lens.

A second aspect of the present invention is a method of making anarticle of manufacture that includes a digitally encoded image and apolymer, including the steps of: printing a digitally encoded image on acomposition that includes a polymer, wherein the polymer forms a lens.

A third aspect of the present invention is a method of making an articleof manufacture that includes a digitally encoded image and a polymer,including the steps of: printing a digitally encoded image on acomposition comprising a polymer, and forming a lens from said polymer.

A fourth aspect of the present invention is a method of making anarticle of manufacture that includes a digitally encoded image and apolymer, including the steps of: printing a digitally encoded image on acomposition comprising at least one monomer, polymerizing said at leastone monomer to form at least one polymer, and forming a lens from saidat least one polymer.

A fifth aspect of the present invention is a method of making an articleof manufacture that includes a digitally encoded image and a polymer,including the steps of: printing an image on at least one first surface,transferring said image to at least one second surface comprising amonomer or a polymer, and forming a lens from said second surface.

A sixth aspect of the present invention is an article of manufacture,including: at least one information storage medium, and at least onedigital image, wherein the at least one digital image comprises at leasta portion of an image or other image.

A seventh aspect of the present invention is a system, including: anarticle of manufacture of the present invention and a printing device.

An eighth aspect of the present invention is a composition of matter,including an ink, dye, vat dye, particle, pigment, reactive dye or diazodye. The composition of matter also includes a binder, monomer, polymer,homopolymer, heteropolymer, copolymer, and initiator, UV initiator,thermal initiator, solvent, dispersant, anti-bacterial agent,anti-microbial agent, anti-fungal agent, disinfectant, thickener orhumectant.

A ninth aspect of the present invention is a method of doing business,including the steps of: obtaining a digital image from a person,database or image and printing said digital image on a lens.

A tenth aspect of the present invention is an article of manufacture,including: a polymer substrate, and a digitally encoded image made withink, wherein the polymer substrate forms a lens, wherein the polymersubstrate is subjected to a pre-treatment process that precedes theapplication of the digitally encoded image to the polymer substrate; andwherein the pre-treatment process results in an enhanced image qualityof the digitally encoded image.

An eleventh aspect of the present invention is a method of making anarticle of manufacture including a polymer substrate and a digitallyencoded image made with ink, wherein the polymer substrate forms a lens,including: subjecting the polymer substrate to a pre-treatment process;and applying the digitally encoded image to the polymer substrate,wherein the pre-treatment process results in an enhanced image qualityof the digitally encoded image.

A twelfth aspect of the present invention is an article of manufacture,including: a polymer substrate and a digitally encoded image made withink comprising reactive components, wherein the polymer substrate formsa lens, wherein the digitally encoded image is applied to the polymersubstrate by ink jet printing; and wherein the reactive component isstored in an ink jet printer cartridge.

DETAILED DESCRIPTION OF THE INVENTION

Definitions

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Generally, the nomenclatureused herein and the laboratory procedures well known and commonlyemployed in the art. Conventional methods are used for these procedures,such as those provided in the art and various general references such asU.S. Pat. Nos. 5,160,463; 5,271,874; 5,018,849; 5,034,166; 5,414,477;Day et al., Current Optometric Information and Terminology, ThirdEdition, American Optometric Association (1980); Howley's CondensedChemical Dictionary (1981); and Federation of Societies for CoatingsTechnology, Glossary of Color Terms, Federation of Societies forCoatings Technology (1981). Where a term is provided in the singular,the inventors also contemplate the plural of that term. The nomenclatureused herein and the laboratory procedures described below are those wellknown and commonly employed in the art. As employed throughout thedisclosure, the following terms, unless otherwise indicated, shall beunderstood to have the following meanings:

“Directly” refers to direct causation of a process that does not requireintermediate steps.

“Indirectly” refers to indirect causation that requires intermediatesteps.

“Digitally Encoded Image” or “Digital Image” refers to an image that hasbeen created or stored in a digital format. A digitally encoded imagecan be made using methods known in the art, such as artistic renditionsor scanning or otherwise translating an image, including a naturallyoccurring image such as the iris of an eye, such as a human eye. Adigitally encoded image can be stored on appropriate storage medium,such as magnetic medium or polymers such as cyclo-olefin copolymers. Aplurality of digitally encoded images can be stored together orseparately to form a database of digitally encoded images that areaccessible individually or in combination. Such digitally encoded imagescan be altered using established methods, such as artistic renditions orimage modulating software. A plurality of images can also be merged toform a new digitally encoded image. A digital image is where a givenimage is presented as made from multiple dots of different colors. Forexample, an image produced by using a scanner or digital camera.Modified digital images may be defined as a digital image that ischanged with a secondary process like polymerization or mixing ofcolored dots.

“Ink” as used herein refers to any colored compound, chemical orstructure, such as a dye, vat dye, particle, pigment, reactive dye,diazo dye and the like. Ink also includes structures that while notcolored give the appearance of color by, for example, diffraction ordeflection (for example) of light by a particle. An ink can be waterbased, monomer based, or solvent based.

“Dye” in the context of inks refers to a variety of dyes as they areknown in the art, such as diazo dyes, such as Diazo 15(4-diazo-(4′-toluyl)-mercapto-2,5-diethoxy benzyene zinc chloride) (U.S.Pat. No. 5,662,706).

“Vat Dye” in the context of inks refers to a variety of vat dyes as theyare known in the art, such as Vat Blue 6(7,16-dichloro-6,15-dihydro-9,14,18-anthrazinetertrone) and Vat Green 1(16,17-dimethyoxydinaphtho (1,2,3, ed: 31, 2′-1′-1-m)perylene-5) (U.S.Pat. No. 5,302,978).

“Particle” in the context of inks refers to a variety of particles asthey are known in the art, such as India Ink.

“Pigment” in the context of inks refers to a variety of pigments as theyare known in the art, such as titanium dioxide, red iron oxide, yellowiron oxide U.S. Pat. No. 5,160,463, Pigment Blue 15 (phthalocyanine blue(CI #74160)), Pigment Green 7 (phthalocyanine green (CI #74260)),Pigment Blue 36 (cobalt blue (CI #77343)) or chromium sesquioxide (U.S.Pat. No. 5,272,010).

“Reactive Dye” in the context of inks refers to a variety of reactivedyes as they are known in the art, such as Reactive Blue No. 4(2-anthra-cene-sulfonic acid,1-amino-4,3((4,6-dichloro-s-triazine-2-yl)amino)-4-sulfoaniline)-9-10-dihydro-9-10-dixo,disodium salt; CAS Reg. 4499-01-8); Reactive Yellow No. 86(1,3-ben-zendisulfonic acid 4-((5 aminocarbonyl-1-ethyl-1,6-dihydro-2-hydroxy-4-methyl-6-oxo-3-pridinyl)azo)-6-(4,6-dichloro-1,2,5-triazine-zyl)amino)-disodiumsalt) (U.S. Pat. No. 5,106,182).

“Solvent” in the context of inks refers to an aqueous, organic orinorganic solvent, such as water, isopropanol, tetrahydrofuran oracetone (U.S. Pat. No. 5,271,874).

“Surfactant” refers to a surfactant as that term is known in the art,such as, for example, acetylene glycol or polyoxyethylene alkyl ether(U.S. Pat. No. 5,746,818 and U.S. Pat. No. 5,658,376, respectively).

“Dispersant” in the context of inks refers to dispersants as they areknown in the art, such as, for example, the Tergitol series from UnionCarbide, polyoxylated alkyl ethers, alkyl diamino quaternary salts or“Pecegal “O”” from GAF (U.S. Pat. No. 5,560,766). Dispersants arepreferably used at between about 0.1% and about 10%, more preferablybetween about 0.5% and about 5%.

“Lens” as used herein refers to a composition of matter that cantransmit light. A lens preferably can act as an optical lens, such as acontact lens. In certain aspects of the present invention, a lens neednot act as an optical lens, such as a contact lens that is used forvanity purposes as opposed to purposes relating to the correction,improvement or alteration of a user's eyesight.

“Contact Lens” refers to a structure that can be placed on or within awearer's eye. A contact lens can correct, improve, or alter a user'seyesight, but that need not be the case. A contact lens can be of anyappropriate material known in the art or later developed, and can be asoft lens, a hard lens or a hybrid lens. A contact lens can be in a drystate or a wet state.

“Soft Lens” refers to a variety of soft lenses as they are known in theart that are characterized as having, for example, at least one of thefollowing characteristics: oxygen permeable, hydrophilic or pliable.

“Hard Lens” refers to a variety of hard lenses as they are known in theart that are characterized as having, for example, at least one of thefollowing characteristics: hydrophobic, gas permeable or rigid.

“Hybrid Lens” refers to a variety of hybrid lenses as they are known inthe art, such as, for example, a lens having a soft skirt and a hardcenter.

“Dry State” refers to a soft lens in a state prior to hydration or thestate of a hard lens under storage or use conditions.

“Wet State” refers to a soft lens in a hydrated state.

“Single color” refers to a discrete color made of one or more ink.

“Multi-colored image” refers to an image that includes more than onesingle color. A multi-colored image can be made using a plurality ofsingle colors. For example, a multi-colored image can be made using twoor more single colors, three or more single colors, or four or moresingle colors, preferably primary colors. The colors can be mixed beforeor during the formation of a multi-colored image, such as during aprinting process, such as printing processes using dispensation, such asink jet printing.

“Transparent” refers to a substantial portion of visible lighttransmitted through a structure, such as greater than or equal to 90% ofincident light.

“Opaque” refers to a substantial portion of visible light reflected orabsorbed by a structure, such as greater than or equal to 90% ofincident light.

“Partially opaque” refers to a combination of transparent and opaque.

“Hydrogel” refers to a polymer that swells in an aqueous solution due tothe absorbance of water. A hydrogel includes water or an aqueoussolution as part of its structure.

“Polymer” refers to a linkage of monomers. Preferably, a polymer is apolymer appropriate for use in lenses, such as contact lenses. A polymercan be, for example, a homopolymer, a heteropolymer, a copolymer, ahydrophobic polymer, a hydrophilic polymer or any combination thereof.

“Hydrophobic Polymer” refers to a polymer that does not absorb anappreciable amount of water or an aqueous solution (see, U.S. Pat. No.5,034,166). “Hydrophilic Polymer” refers to a polymer that absorbs anappreciable amount of water or an aqueous solution (see, U.S. Pat. No.5,034,166). Lens forming materials that are suitable in the fabricationof contact lenses are illustrated by one or more of the following U.S.Pat. Nos. 2,976,576; 3,220,960; 3,937,680; 3,948,871; 3,949,021;3,983,083; 3,988,274; 4,018,853; 3,875,211; 3,503,942; 3,532,679;3,621,079; 3,639,524; 3,700,761; 3,721,657; 3,758,448; 3,772,235;3,786,034; 3,803,093; 3,816,571; 3,940,207; 3,431,046; 3,542,461;4,055,378; 4,064,086; 4,062,624; and 5,034,166.

“Hydrophilic Monomer” refers to monomers used to make soft lenses, suchas hydroxyethylmethacrylate, methacrylic acid, or N-vinylpyrrolidone(U.S. Pat. No. 5,271,874; U.S. Pat. No. 5,272,010). “HydrophilicMonomer” refers to monomers used to make hard lenses, such asmethylmethacrylate, ethoxyethylmethacrylate, styrene, or silicone (U.S.Pat. No. 5,271,874; U.S. Pat. No. 5,272,010).

“Homopolymer” refers to a polymer comprising a single type of monomersuch as hydroxyethylmethacrylate.

“Heteropolymer” refers to a polymer comprising more than one type ofmonomer such as hydroxyethylmethacrylate and methacrylic acid.

“Copolymer” refers to the use of two different polymers to make apolymer chain.

“Acrylic Polymer” or “Acrylics” refers to a variety of polymer of thatgenus and species as they are known in the art, such as, for example,hydroxyethylmethacrylate.

“Silicone Polymer” or “Silicones” refers to a variety of polymers ofthat genus and species as they are known in the art, such as, forexample Tris (such as Tris(pentamethyldisiloxyanyl)-3-methacrylate-propylsilane or3-methacryloxypropy tris(trimethylsiloxy)silane).

“Polycarbonate Polymer” or “Polycarbonate” refers to a variety ofpolymers of that genus and species as they are known in the art, suchas, for example Lexan.

“Initiator” in the context of polymerization refers to an initiator asthat term is known in the art, such as, for example, a chemical thatstarts a polymerization reaction.

“UV Initiator” in the context of polymerization refers to a UV initiatoras that term is known in the art, such as, for example, a chemical thatbecomes reactive or active with the adsorption of energy, such as UVenergy, such as, for example benzoin methyl ether.

“Binder” or “bonding agent” refers to compounds used perform thefunction of increasing the interaction between moieties, such as betweena dye and a polymer or monomer or between monomers and polymers such asthose terms are known in the art. Examples of binders or binding agentsare hexamethylene diisocyanate or other isocyanate compounds.

“Thickener” refers to a compound that is used to increase the viscosityof a liquid or partially liquid mixture or solution such as that term isknown in the art. An example of a thickener is polyvinyl alcohols.

“Anti-kogating agent” or “non-kogating agent” refers to compounds thatfacilitate printing processes that utilize nozzles, such as such termsare known in the art.

“Dispersant” refers to a surface-active agent added to a suspendingmedium to promote the distribution and separation of fine or extremelyfine solid particles.

“Thermal Initiator” in the context of polymerization refers to a thermalinitiator as that term is known in the art, such as, for example, achemical that becomes active or reactive with the absorption of heatenergy, such as, for example, Vazo-64 or azobisisobutyronitrile.

“Anti-Bacterial Agent” refers to a compound or composition that can actas a bactericidal or bacteriostatic or can reduce the growth rate of abacteria such as tetrabutylammonium chloride.

“Anti-Fungal Agent” refers to a compound or composition that can act asa fungicidal or fungistatic or can reduce the growth rate of a fungisuch as benzalkonium chloride salicylic acid.

“Disinfectant” refers to a compound or composition that can reduce thetype, number or diversity of microorganisms.

“Humectant” refers to compounds that reduce evaporation, such asethylene glycol.

“Printing” refers to the application of at least one ink to a surface orstructure to form an image. Printing can use any appropriate device ormethod known in the art of later developed for a particular purpose.

“Printing Device” refers to any appropriate device for printing an imageon a surface or structure known in the art or later developed for aparticular purpose. Preferably, a printing device includes thedispensation of microdroplets of liquid that includes an ink that forman image. The size or volume of the microdroplets can vary, butgenerally the smaller the microdroplet, the higher the quality of theimage produced. Preferred microdroplets are between about 1 nanoliterand about 100 microliters, preferably between about 10 nanoliters andabout 10 microliters or between about 100 nanoliters and about 1microliter.

“Ink Jet Printing” refers to printing using a printing device thatcomprises at least one ink jet. Ink jet printing can use a single coloror can use a plurality of colors. For example, ink jet printing can usea printing device that contains a plurality of different colored inksthat can be provided separately. In this aspect of the invention, theinks are preferably at least two, at least three or at least fourprimary colors and black that can be mixed to form a very large numberof different colors. Such printing devices are commercially availablesuch as through, for example, Hewlett Packard Corporation (such asDeskJet 560C printer cartridges) and Encad Corporation. Ink can beapplied to a surface more than once to obtain the desired intensity, hueor other color characteristic.

“Piezo Printing” refers to printing using a printing device thatcomprises at least one piezo printing structure. Such piezo printingstructures are known in the art, such as, for example, those availablethrough Packard Instruments and Hewlett Packard Corporation or CanonInc.

“Thermal Printing” refers to printing using a printing device thatcomprises at least one thermal printing structure. Such thermal printingstructures are known in the art, such as, for example, those availablethrough Hewlett Packard Corporation.

“Laser Printing” refers to printing using a printing device that uses atleast one laser printing structure. Such printing structures are knownin the art, such as, for example, those available through Cannon orHewlett Packard Corporation.

“Pad Transfer Printing” refers to printing using a pad transfer printingdevice. Such pad transfer printing devices are known in the art,particularly for printing in the field of contact lenses. Briefly, animage is placed or printed on a pad transfer device and the image on thepad transfer device is transferred to another surface, such as a polymeror lens (U.S. Pat. No. 3,536,386 to Spivack, issued Oct. 27, 1970; U.S.Pat. No. 4,582,402 to Knapp, issued Apr. 15, 1986; U.S. Pat. No.4,704,017 to Knapp, issued Nov. 3, 1987; U.S. Pat. No. 5,034,166 toRawlings et al., Jul. 23, 1991; U.S. Pat. No. 5,106,182 to Briggs etal., issued Apr. 21, 1992; U.S. Pat. No. 5,352,245 to Su et al., issuedOct. 4, 1994; U.S. Pat. No. 5,452,658 to Shell, issued Sep. 26, 1995 andU.S. Pat. No. 5,637,265 to Misciagno et al., issued Jun. 10, 1997).

“Impregnation” refers to an ink being contacted with a surface, such asa polymer, and the ink diffuses into the polymer where it is reacted toprecipitate to a size larger than the average pore size of the polymer(EP 0357062 to Pfortner, published Mar. 7, 1990).

“Photolithography” refers to a process as it is known in the art, suchas wherein at least one photosensitive ink is used to provide a desiredimage using a mask that blocks light.

“Chemical Bond” refers to a covalent bond or non-covalent bond. Undercertain circumstances, inks can form chemical bonds with polymers ormonomers if the reactive groups on each are appropriate (EP 0393532 toQuinn, published Oct. 24, 1990 (referring to U.S. Pat. No. 4,668,240 toLoshaek and U.S. Pat. No. 4,857,072); U.S. Pat. No. 5,272,010 to Quinn,issued Dec. 21, 1993;

“Polymer-Polymer Bond” refers to two polymers forming covalent ornon-covalent bonds, such as by cross linking polymers formed between twopolymers, such as hydroxyethyl methylacrylate andehtyleneglycoldimethacrylate.

“Pattern” refers to a predetermined image (U.S. Pat. No. 5,160,463 toEvans et al., issued Nov. 3, 1992; U.S. Pat. No. 5,414,477 to Jahnke,issued May 9, 1995;).

“At least two separate colors or a mixture thereof,” “at least threeseparate colors or a mixture thereof,” or “at least four separate colorsor a mixture thereof” refers to the use of inks of different colorsbeing provided in separate containers or separate portions within acontainer. The colors are preferably primary colors or fundamentalcolors and black, more preferably black, cyanine, magenta and yellow.The inks can be mixed in different proportions (including zero) toobtain a very large spectrum of colors. The mixing can occur within aprinting structure, for example, before the ink is dispensed in aprinting process. Alternatively, the mixing can occur outside of aprinting structure, for example, after the ink is dispensed in aprinting process. Furthermore, a combination of the foregoing can alsooccur.

“Dry State” refers to a polymer that is not fully hydrated.

“Wet State” refers to a polymer that is fully hydrated.

“Forming a Lens” or “Fabricating a Lens” refers to any method orstructure known in the art or later developed used to form a lens. Suchforming can take place, for example, using cast-molding, spin-casting,cutting, grinding, laser cutting, stamping, trimming, engraving, etchingor the like (U.S. Pat. No. 4,558,931 to Fuhrman, issued Dec. 17, 1985).

“Cast-Molding” in the context of forming a lens refers to the formationof at least a portion lens using a mold (U.S. Pat. No. 3,536,386 toSpivak, issued Oct. 27, 1970; U.S. Pat. No. 3,712,718 to LeGrand et al.,issued Jan. 23, 1973; U.S. Pat. No. 4,582,402 to Knapp, issued Apr. 15,1986; U.S. Pat. No. 4,704,017 to Knapp, issued Nov. 3, 1987; U.S. Pat.No. 5,106,182 to Briggs et al., issued Apr. 21, 1992; U.S. Pat. No.5,160,463 to Evans et al., issued Nov. 3, 1992; U.S. Pat. No. 5,271,874to Osipo et al., issued Dec. 21, 1993 and EP 0357062 to Pfortner,published Mar. 7, 1990)

“Spin-Casting” in the context of forming a lens refers to the formationof a lens using centrifugal force (U.S. Pat. No. 3,557,261 to Wichterle,issued Jan. 19, 1971 and U.S. Pat. No. 5,034,166 to Rawlings et al.,issued Jul. 23, 1991).

“Information Storage Medium” refers to any medium of expression that canstore information in any appropriate format either permanently ortransiently. Preferred information storage medium includes paper,electronic medium, magnetic medium or polymers, such as cyclo-olefincopolymers.

“Electronic Medium” refers to information storage medium that can storeinformation in electronic form. For example, electronic medium includesmagnetic storage medium, such as diskettes.

“Machine Readable Format” refers to information stored on or within aninformation storage medium in a form, language or arrangement such thata machine, such as a central processing unit (CPU) can access and usethe information.

“Database” refers to a collection of information, such as digitalimages. The information is preferably provided on or within aninformation storage medium and can be separate from or integral with acentral processing unit.

Other technical terms used herein have their ordinary meaning in the artthat they are used, as exemplified by a variety of technicaldictionaries.

Introduction

The present invention recognizes that lenses, such as contact lenses,can be tinted using ink that includes polymers or polymerizablemonomers, preferably the same monomers used to make the lens. The inkcan be used to make images on or within the lens. Images made usingthese inks are preferably digital and can be used in a variety ofprinting methods, including ink-jet printing.

As a non-limiting introduction to the breath of the present invention,the present invention includes several general and useful aspects,including:

-   1) an article of manufacture, including: a polymer and a digitally    encoded image made with ink, wherein the polymer forms a lens;-   2) a method of making an article of manufacture that includes a    digitally encoded image and a polymer, including the steps of:    printing a digitally encoded image on a composition that includes a    polymer, wherein the polymer forms a lens, wherein such lenses can    optionally include indentation structures to facilitate localizing    inks used to make the digitally encoded image;-   3) a method of making an article of manufacture that includes a    digitally encoded image and a polymer, including the steps of:    printing a digitally encoded image on a composition comprising a    polymer, and forming a lens from said polymer;-   4) a method of making an article of manufacture that includes a    digitally encoded image and a polymer, including the steps of:    printing a digitally encoded image on a composition comprising at    least one monomer, polymerizing said at least one monomer to form at    least one polymer, and forming a lens from said at least one    polymer;-   5) a method of making an article of manufacture that includes a    digitally encoded image and a polymer, including the steps of:    printing an image on at least one first surface, transferring said    image to at least one second surface comprising a monomer or a    polymer, and forming a lens from said second surface;-   6) an article of manufacture, including: at least one information    storage medium, and at least one digital image, wherein the at least    one digital image comprises at least a portion of an image or other    image;-   7) a system, including: an article of manufacture of the present    invention and a printing device;-   8) a composition of matter, including an ink, dye, vat dye,    particle, pigment, reactive dye, or diazo dye. The composition of    matter also includes a binder, bonding agent, monomer, polymer,    homopolymer, heteropolymer, copolymer, and initiator, UV initiator,    thermal initiator, solvent, dispersant, surfactant, anti-bacterial    agent, anti-microbial agent, anti-fungal agent, disinfectant,    thickener or humectant;-   9) a method of doing business, including the steps of: obtaining a    digital image from a person, database or image and printing said    digital image on a lens.-   10) an article of manufacture, including: a polymer substrate, and a    digitally encoded image made with ink, wherein the polymer substrate    forms a lens, wherein the polymer substrate is subjected to a    pre-treatment process that precedes the application of the digitally    encoded image to the polymer substrate; and wherein the    pre-treatment process results in an enhanced image quality of the    digitally encoded image;-   11) a method of making an article of manufacture including a polymer    substrate and a digitally encoded image made with ink, wherein the    polymer substrate forms a lens, including: subjecting the polymer    substrate to a pre-treatment process; and applying the digitally    encoded image to the polymer substrate, wherein the pre-treatment    process results in an enhanced image quality of the digitally    encoded image; and-   12) an article of manufacture, including: a polymer substrate and a    digitally encoded image made with ink comprising reactive    components, wherein the polymer substrate forms a lens, wherein the    digitally encoded image is applied to the polymer substrate by ink    jet printing; and wherein the reactive component is stored in an ink    jet printer cartridge.

These aspects of the invention, as well as others described herein, canbe achieved by using the methods, articles of manufacture andcompositions of matter described herein. To gain a full appreciation ofthe scope of the present invention, it will be further recognized thatvarious aspects of the present invention can be combined to makedesirable embodiments of the invention.

I Lens with Digitally Encoded Image

The present invention includes an article of manufacture, including: apolymer and a digitally encoded image comprising at least one ink,wherein the polymer forms a lens.

Digitally Encoded Image

The digitally encoded image can include a single color image or amulti-colored image. The single color image preferably comprises oneink, but that need not be the case because many inks have similar colorsand different colored inks can be combined to produce an ink with acolor different from the individual inks used to make the combination.The multi-colored image is preferably made using a plurality of inkseither alone or in combination.

The digitally encoded image can be transparent, opaque, or partiallyopaque. For transparent digitally encoded images, the ink within theimage does not substantially interfere with the transmission of lightthrough the polymer. For opaque digitally encoded images, the ink withinthe digitally encoded image substantially interferes with thetransmission of light through the polymer. When the lens is a contactlens, opaque digitally encoded images can substantially block thenatural color of the contact lens wearer's iris. Ink used to create anopaque digitally encoded image can include materials such as particles,for example as mica or ground oyster shells or particulates, in a typeand amount sufficient to make the digitally encoded image opaque.Another alternative is a pigment, vat dye, diazo dye or reactive dye.For partially opaque digitally encoded images, the ink within thedigitally encoded image can include materials such as particles andparticulates, such as mica, ground oyster shells or particulates, in atype and amount sufficient to partially block the transmission of lightthrough the digitally encoded image. Partially blocking the transmissionof light, in this instance, refers to the ability of the digitallyencoded image to allow a portion of incident light to transmit through adigitally encoded image.

Ink

Inks used in the present invention can include any single coloredcompound or composition or any combination of colored compounds orcompositions. Inks can be provided in water, monomer or solvents,preferably at a concentration between about 0% and greater than about99.5% or between about 0.01% and about 99.5%, preferably between about0.1% and about 90% or between about 1% and about 80%, and morepreferably between about 10% and about 60% or between about 20% andabout 40%. Inks can also include particles or particulates, preferablyat a concentration of between about 0% and about 5% or between about0.01% and about 5%, preferably between about 0.1% and about 4% orbetween about 1% and about 3% to render a digitally encoded image opaqueor partially opaque. Examples of inks include dyes, vat dyes, particles,pigments, reactive dyes or diazo dyes. As discussed herein, thecharacteristics and compositions including inks and other componentsinclude inks that are part of an article of manufacture of the presentinvention, such as a lens, such as a contact lens, and also includecompositions that include at least one ink that can be used to make anarticle of manufacture of the present invention.

Inks can include water, monomer, polymer or an appropriate solvent inorder for the ink to be suitable in the making of a digitally encodedimage. An appropriate solvent is a solvent that is compatible with thecreation of a digitally encoded image on or within a surface, such as onor within a polymer. For example, solvents appropriate for polymers usedto make lenses, such as contact lenses, include, but are not limited toisopropanol, water, acetone or methanol, either alone or in combinationand can include a monomer. Appropriate concentrations of solvents arebetween about 0% and greater than about 99.5% or between about 0.1% andabout 99.5%, preferably between about 1% and about 90% or between about10% and about 80%, and more preferably between about 20% and about 70%or between about 30% and about 60%. Different polymers, monomer and inkshave different tolerances and reactivities to different solvents. Thus,appropriate matches between solvent and polymer, monomer and ink shouldbe considered. For hydrogel polymers, adjustment in swelling ratios maybe achieved with a variety of concentrations of solvents.

An ink can also include a monomer, polymer, homopolymer, heteropolymer,or copolymer. In a preferred aspect of this embodiment of the presentinvention, an ink includes a monomer that can be polymerized to form apolymer using polymerization methods appropriate for a given monomer,mixtures thereof, or polymers, or mixtures thereof. Monomers can also beused to decrease the viscosity of the ink. Alternatively, the ink caninclude a polymer such that the viscosity of the ink is increased.Alternatively, the ink can include polymer and monomer. Appropriateconcentrations of monomers are between about 5% and greater than 99%,preferably between about 25% and about 75%, and more preferably betweenabout 35% and about 60%. Appropriate concentrations of polymers arebetween about 0% and about 50%, preferably between about 5% and about25%, and more preferably between about 10% and about 20%. When monomersand polymers are mixed, the total concentration of monomer and polymerare lo between about 10% and greater than 99%, preferably between about25% and about 75% and more preferably between about 35% and about 65%.

The viscosity of a solution including an ink can be as high as betweenabout 500 centipoise and about 5,000 centipoise and is preferablybetween about 1 to about 200 centipoise or between about 10 and about 80centipoise, preferably between about 20 and about 70 centipoise orbetween about 30 and about 60 centipoise or between about 1 and about 10centipoise. Solutions having low viscosity tend to be “runny” whendispensed, and can allow different colors to merge and blend, resultingin an image with a more natural appearance. Such blending can beenhanced using a variety of methods, including sonication or vibrationat appropriate duration and frequency to promote appropriate blending.Solutions having too low a viscosity can result in images that are too“runny” and thus have potentially undesirable characteristics, such aspooling of ink in a digitally encoded image or spreading of ink to anunintended location. Solutions having too high a viscosity may not beeasily dispensed using a variety of printing structures, such as inkjets and thus may not be appropriate for the present invention.Furthermore, solutions having high viscosity can tend to “bead” on asurface and not blend with the surrounding environment, includingsurrounding droplets or beads of ink. Under these circumstances, the inkmay form unnatural appearing images (see, for example, U.S. Pat. No.5,160,463 and U.S. Pat. No. 5,414,477). Agents such as thickeners ordiluents (including appropriate solvents) can be used to adjust theviscosity of the ink.

An ink that includes at least one monomer can also include apolymerization initiator, so that once an ink that includes at least onetype of monomer is dispensed, the polymerization of the monomer in theink is initiated. The number, type and amount of initiator is a matterof choice depending on the type of monomer or monomers in the ink.Appropriate initiators include, but are not limited to, UV initiatorsthat initiate polymerization by UV irradiation, thermal initiators thatinitiate polymerization by thermal energy.

An ink can also include a dispersant to allow uniform composition of inkin a container. Dispersants are preferably provided at an appropriateconcentration, such as between about 1% and about 10%.

An ink can also include at least one anti-microbial agent or antisepticagent to kill or reduce the number or multiplication microbial agents,reduce the number of microbial agents, or keep microbial agents frommultiplying. Preferred anti-microbial agents include anti-bacterialagents, anti-fungal agents and disinfectants. Preferably, suchanti-microbial agents, anti-bacterial agents, anti-fungal agents anddisinfectants are provided at an appropriate concentration such asbetween about 0% and about 1%.

An ink can also include at least one humectant such as1,3-diozane-5,5-dimethanol (U.S. Pat. No. 5,389,132) at an appropriateconcentration. Preferably, the range of concentration of a humectant isbetween about 0% and about 2%.

An ink can also include at least one antioxidant agent or a lowcorrosion agent, such as alkylated hydroquinone, at an appropriateconcentration, such as between about 0.1% and about 1% (U.S. Pat. No.4,793,264). An ink can also include a non-kogating agent or non-kogatingagent, such as 2-methyl-1,3-propanediol at an appropriate concentration,such as between about 0% and about 1%. An ink can also include anevaporation retarding agent, such as, for example, diethylene glycerolor ethylene glycol at between about 0% and about 2% (U.S. Pat. No.5,389,132).

A preferred ink can have the following composition:

Component Percentage Monomer   0% to 99% Pigment and/or colorant  0.1%to 15% and/or reactive dye Initiator 0.01% to 2% Solvent   0% to 80%Binder or Bonding Agent   0% to 10% Thickener   0% to 1% Anti-kogatingAgent   0% to 1% Humectant   0% to 1% Surfactant   0% to 10%Cross-linker   0% to 1% Dispersant   0% to 10%Printing

The digitally-encoded image is preferably applied to a structure, suchas a lens, using a printing method or printing structure. The digitallyencoded image can be stored digitally in at least one informationstorage medium, such as an electronic medium. The stored digitallyencoded image can be printed using printing structures and printingmethods that can convert the stored digitally encoded image into aprinted image using an appropriate interface. For example, a centralprocessing unit can include a stored digitally encoded image. Softwarecan interface the stored digitally encoded image with a printingstructure such that the printing structure prints the digitally encodedimage. Such interfaces are known in the art, such as those used indigital printing processes that use ink-jets (Hewlett Packard; Encad)(see, for example, FIG. 1).

Preferred printing methods and printing structures include, but are notlimited to, ink-jet printing, piezo printing, thermal printing, bubblejet printing, pad-transfer printing, impregnation, photolithography andlaser printing. Ink-jet printing can use appropriate ink-jet printingstructures and ink-jet printing methods as they are known in the art orlater developed. For example, appropriate ink-jet printing structuresinclude, but are not limited to HP Desk Jet 612 or Canon color bubblejet BJC1000 color printer hardware. Furthermore, appropriate ink-jetprinting methods, include, but are not limited to thermal ink jetprinting, piezo printing or bubble jet printing.

Ink-jet printing can include piezo printing structures and piezoprinting methods as they are known in the art or later developed. Forexample, appropriate piezo printing structures include, but are notlimited to Canon color bubble jet printer BJC1000.

Ink-jet printing can include thermal printing structures and thermalprinting methods as they are known in the art or later developed. Forexample, appropriate thermal printing structures include, but are notlimited to HP Deskjet 612 color printer.

Ink-jet printing can include bubble jet printing structures and bubblejet printing methods as they are known in the art or later developed.For example, appropriate thermal bubble jet structures include, but arenot limited to Canon BJC1000 color printer.

Pad-transfer printing can include pad-transfer printing structures andpad-transfer printing methods as they are known in the art or laterdeveloped. For example, appropriate pad-transfer printing structuresinclude, but are not limited to Tampo-type printing structures (Tampovario 90/130), rubber stamps, thimbles, doctor's blade, direct printingor transfer printing as they are known in the art.

Impregnation printing can include impregnation printing structures andimpregnation printing methods as they are known in the art or laterdeveloped. For example, appropriate impregnation printing structuresinclude, but are not limited to applying solubilized vat dyes, maskingdevice, developer and the like.

Photolithography printing can include photolithographic printingstructures and photolithography printing methods as they are known inthe art or later developed. For example, appropriate photolithographyprinting structures include, but are not limited to applying diazo dyes,masking devices, developers and the like.

Laser printing can include laser printing structures and laser printingmethods as they are known in the art or later developed. For example,appropriate laser printing structures include, but are not limited to HPLaser Jet printer hardware, particularly the 4L, 4M series.

More than one printing structure or more than one printing method can beused to make a digitally encoded image of the present invention. Forexample, ink-jet printing and pad transfer printing can be used incombination.

Digitally encoded images can be printed on the surface of a structure,such as on the surface of a lens, such as on the surface of a contactlens. In this aspect of the present invention, the printing structuresand printing methods deposit ink onto a surface. The ink can then dry toproduce a non-transient image, or monomers or polymers within the inkcan be polymerized to produce a non-transient image. In the latterinstance, the monomers or polymers are preferably the same or result inthe same polymer that comprises the surface. Digitally encoded imagescan be printed on at least one surface of a structure. For example, ifthe structure is a lens, such as a contact lens, a digitally encodedimage can be printed on either or both sides of the contact lens.Printing methods preferred for this type of printing include, but arenot limited to thermal inkjet or bubble jet printing.

As depicted in FIG. 2, digitally encoded images can also be trappedwithin a structure, such as a lens, such as a contact lens. In thisaspect of the present invention, the image can be trapped within astructure using laminate printing, including sandwich laminate printing.For example, an image is printed on a surface, such as a first portionof a lens, then a second portion of a structure, such as a secondportion of a lens, is attached to the first portion of a lens such thatthe image is trapped between the first portion of a structure and thesecond portion of a structure.

Preferably, the first portion of a structure includes a polymer and thedigital image includes a monomer. The monomer can be polymerized suchthat the digitally encoded image becomes non-transient and substantiallyimmobile. Then the second portion of a lens is attached to the firstportion of a structure such that the digitally encoded image becomestrapped between the first portion of the structure and the secondportion of a structure. In this aspect of the present invention, thedigitally encoded image preferably includes a monomer that can bepolymerized to form a polymer, preferably a polymer that is included inthe first portion of a structure or the second portion of a structure,preferably both.

In a preferred aspect of the present invention, the first portion of astructure is a non-polymerized monomer or semi-polymerized polymer thatincludes monomer onto which the digitally encoded image, whichpreferably comprises the same monomer as the first portion of astructure, is printed. This composite structure can be partially orfully polymerized and a second portion of a structure attached theretoto entrap the digitally encoded image therein. In the alternative, thesecond portion of a structure, which preferably includes monomer andoptionally polymer, preferably the same as the first portion of a lensand the digitally encoded image, is contacted with this first portion ofa structure and digitally encoded composite such that the digitallyencoded image is trapped between the first portion of a structure andthe second portion of a structure. The resulting laminate compositestructure includes a digitally encoded image trapped within thestructure. In one aspect of the present invention a partiallypolymerized layer of ink is contacted with a monomer, or alternatively amonomer is partially polymerized and contacted with a layer of ink. Eachcombination can be partially polymerized and transferred to a primarysurface and fully polymerized such that the polymerized layer of ink issandwiched in between a polymer layer and the primary polymerizedsurface (see, for example, FIG. 3).

The laminate composite structure can be fashioned into a lens usingmethods described herein and as they are known in the art or laterdeveloped, such as, for example, laser cutting, stamping, grinding,polishing or the like. In the alternative, the laminate compositestructure made using the foregoing methods results in a lens. Forexample, the laminate composite can be made in a mold that has the shapeof a lens. Such molds are known in the art and have been describedherein. In the alternative, the method used to make the laminate canform a lens, such as spin-casting methods.

Lenses made using spin casting are preferable in the present method. Inthe alternative, other appropriate methods, such as those describedherein, known in the art, or later developed, that can form at least aportion of a lens can also be used. In this aspect of the presentinvention, a first portion of a structure is printed with a digitallyencoded image and the second portion of a structure is added thereon toform a laminate structure. Spin-casting or other lens forming methodsand polymerizing can optionally take place any time during this processand the first portion the structure, the second portion of a structureand the digitally encoded image can be in various states ofpolymerization, such as non-polymerized, partially polymerized orpolymerized. Optionally, the digitally encoded image need not includemonomer or polymer.

For example, a first portion of a structure can be non-polymerized,polymerized or partially polymerized and can be spin-cast (or other lensforming method) or not spin-cast (or other lens forming method). Adigitally encoded image including or not including a monomer and/or apolymer can be printed on the first portion of a lens to form acomposite. This composite can be polymerized, not polymerized orpartially polymerized and can optionally be spin-cast (or other lensforming method) or at least a portion of a lens formed by anotherappropriate method (the optional polymerization and optionalspin-casting (or other lens-forming method) can take place in eitherorder). This composite is then contacted with a second portion of astructure that can be polymerized, partially polymerized ornon-polymerized and then can be optionally spin-cast (or other lensforming method) to form a portion of a lens to form a compositelaminate. The composite laminate, or at least a portion thereof, is orare optionally polymerized. Preferably, the first portion of astructure, the digitally encoded image and the second portion of astructure all share at least one common monomer or polymer, but thatneed not be the case.

One example of this method includes a first portion of a structuredispensed into a receiving structure such as a mold, wherein the firstportion of a structure is non-polymerized, partially polymerized orpolymerized and is not spin-cast (or other method of forming at least aportion of a lens). The digitally encoded image is printed on the firstportion of a structure, wherein the digitally encoded image optionallyincludes a monomer and/or a polymer to form a composite structure. Asecond portion of a structure is contacted with the composite structure,wherein the second portion of a structure is non-polymerized, partiallypolymerized or polymerized to form a laminate composite. The laminatecomposite is then spin-cast (or other method of forming at least aportion of a lens).

Another example of this method includes a first portion of a structuredispensed into a receiving structure, such as a mold, wherein the firstportion of a structure is non-polymerized or partially polymerized andis optionally spin-cast (or other method of forming at least a portionof a lens) and is optionally polymerized. The digitally encoded image isprinted on the first portion of a structure, wherein the digitallyencoded image optionally includes a monomer and/or a polymer to form acomposite structure and is optionally spin-cast (or other method offorming at least a portion of a lens) and optionally polymerized. Asecond portion of a structure is contacted with the composite structure,wherein the second portion of a structure is non-polymerized, partiallypolymerized or polymerized to form a laminate composite. The laminatecomposite is optionally spin-cast (or other method of forming at least aportion of a lens). Preferably, the first portion of a structure andsecond portion of a structure include the same or similar monomer andpolymer and are partially polymerized such that a polymerization (suchas a final polymerization of a laminate structure) results in arelatively or substantially “seamless” laminate structure (fused orconnected). Preferably, the digitally encoded also includes the same orsimilar monomer and polymer (non-polymerized or partially polymerized)so that a polymerization (such as a final polymerization of a laminatestructure) results in a relatively or substantially “seamless” laminatestructure.

During this course of this method, the digitally encoded image can forma chemical bond with either or both of the first portion of a structureand the second portion of a structure. In this instance, the digitallyencoded image comprises an ink that can form such a chemical bond.

Also, the digitally encode image can form a polymer-polymer bond witheither one or both the first portion of a structure and second portionof a structure. In this instance, the digitally encoded image includes amonomer or polymer that formed a polymeric bond with at least one of thefirst portion of a structure and second portion of a structure.

In this aspect of the invention, the digitally encoded image preferablyincludes at least one pattern. The pattern can be any pattern, includingnaturally and non-naturally occurring patterns. For example, a naturallyoccurring pattern can include a fractile-like pattern. Non-naturallyoccurring patterns can include geometric patterns or non-geometricpatterns, such as are used in vanity contact lenses. A digitally encodedimage can include at least one color, but preferably includes aplurality of colors. A digitally encoded image preferably includes atleast a portion of an image of an eye, such as the iris of an eye, suchas the iris of a human eye.

The image can include at least one color, but preferably includes two ormore colors. The colors used in the image can be derived from a mixtureof separate colors, such as two or more separate colors, three or moreseparate colors or four or more separate colors. For the purposes ofthis aspect of the invention, black is considered a separate color. Theseparate colors are preferably primary colors that can be mixed indifferent proportions to form a wide array of colors on an image.

Polymers and Lenses

Structures, such as lenses, of the present invention preferably includeat least one polymer. When the structure of the present invention is alens, such as a contact lens, the at least one polymer is preferably apolymer that is compatible with the eye. Preferable polymers for use inmaking contact lenses include, but are not limited to acrylics,silicones, polycarbonates and others known in the art or laterdeveloped. Polymers useful in the present invention can be hydrophobicor hydrophilic. In the case of hydrophilic polymers, the polymerpreferably forms a hydrogel. Generally, polymers used to make contactlenses result in “hard lenses,” “soft lenses” or “hybrid lenses” asthose terms are known in the art.

II Method of Making a Lens with a Digitallt Encoded Image-I

The present invention also includes a method of making an article ofmanufacture that includes a digitally encoded image and a polymer,including the steps of printing a digitally encoded image on acomposition that includes a polymer, wherein the polymer forms a lens.The polymer can be any polymer, but is preferably a polymer in a wetstate or a dry state, such as polymers used in the manufacture oflenses, such as contact lenses.

The article of manufacture is made by providing a composition thatincludes a polymer upon which the digitally encoded image is to beprinted. The polymer is preferably a polymer used to make lenses, suchas contact lenses, and include, but are not limited to, hydrophobicpolymers, hydrophilic polymers, homopolymers, heteropolymers,copolymers, acrylic polymers, silicone polymers or polycarbonatepolymers either alone or in combination. One preferred lens includes thefollowing: HEMA (hydroxyethyl methacrylate), EOEMA(ethoxyethylmethacrylate, MAA (methacrylic acid), EGDMA (ethyleneglycoldimethacrylate), Vazo-64 (azobisisobutyronitrile), BME (benzoinmethylether), IPA (isopropyl alcohol), THF (tetrahydrofuran), Mercap-2(mercaptoethanol), c-pentanone (cyclopentanone) and MEHQ (methylethylhydroquinone) (see U.S. Pat. No. 5,271,874).

In this aspect of the present invention, the polymer at least in partforms a lens, such as a contact lens, such as a soft contact lens, ahard contact lens or a hybrid contact lens. It is the structure thatforms at least in part a lens that a digitally encoded image is printed.Preferably, the digitally encoded image is printed on the lens and canbe printed on either or both sides of the lens. The digitally encodedimage can be printed on the entire lens or a portion thereof. Forexample, the digitally encoded image can depict the iris of an eye suchthat the area corresponding the pupil of the eye is not printed.

The digitally encoded image is preferably encoded electronically, suchas in a database. The digitally encoded image can be prepared by anyappropriate method, such as by scanning an image into a processing unitusing appropriate scanning and storage hardware and software. Thedigitally encoded image can be selected and can be conveyed to aprinting device as an electronic signal using appropriate hardware andsoftware.

The digitally encoded image is preferably printed using a printingdevice that is capable of producing a digital image, such as an ink jetprinting device, a piezo printing device, a thermal printing device or alaser printing device. The printing devices preferably include at leastone ink, wherein if more than one ink is present in such printingdevice, the different inks are provided in separate containers orseparate portions of the same containers, such as provided in HewlettPackard Color DeskJet printer cartridges (HP51649A).

An ink preferably contains at least one monomer, such as a hydrophobicmonomer or hydrophilic monomer that preferably corresponds to a polymerthat is included in the lens. The ink can also include a variety ofother components, such as an appropriate initiator, such as a UVinitiator or a thermal initiator to initiate polymerization of themonomer after being dispensed by a printing device on a polymer. An inkcan optionally also include at least one of a binder, an ant-bacterialagent, an anti-fungal agent, a disinfectant, or a humectant at anappropriate concentration for the intended function. Preferably inksinclude, but are not limited to, pigment black 7 (carbon black), pigmentblack 11 (iron oxide), pigment brown 6 (iron oxide), pigment red 101(iron oxide), pigment yellow 42 (iron oxide), pigment while 6 (titaniumdioxide), pigment green 17 (chromium oxide), pigment blue 36 (chromiumaluminum cobaltous oxide), pigment blue 15 (copper phthaloxyanine),pigment violet 23 (3,amino-9-ethyl carbazole-chloronil) (U.S. Pat. No.5,302,479), Millikan ink yellow 869, Millikan ink blue 92, Millikan inkred 357, Millikan ink black 8915-67 (see U.S. Pat. No. 5,621,022).

Preferably, four separate ink colors, which can include one or moreindividual inks, are used in a printing device FIG. 1. The four inkscorrespond to black, magenta, yellow and cyan. The printing device canmix these inks to provide a wide diversity of colors for use in theprinting process. A typical ink formulation includes: monomer (HEMA),initiator (BME), crosslinker (EGDMA), pigment #1 (phthalocyanine blue),diluent (glycerine), solvent (isopropanol), pigment #2 (titaniumdioxide), dispersant (polyvinyl alcohol), humectant (ethylene glycol),co-monomer (methacrylic acid), inhibitor (MEHQ), anti-kogating agent(methylpropanediol) and anti-oxidant (alkylated hydroquinone). Themonomer can also be a mixture of two or more monomers. A preferred mixof monomers that results in a clear polymer, such as for a clear contactlens, includes monomer HEMA (hydroxyethyl methacrylate), monomer EOEMA(ethoxyethylmethacrylate), monomer MAA (methacrylic acid). Optionallyincluded is at least one of the following: crosslinker EGDMA (ethyleneglycoldimethacrylate), initiator Vazo 64 (azobisisobutyronitrile),solvent isopropyl alcohol, inhibitor MEHQ (methyletherhydroquinone) anddiluent glycerine. All components are at appropriate concentrations fortheir intended purpose.

Optionally, a printing device can include a mixture as described abovewithout an ink that can be dispensed along with at least one ink in aseparate container such that the ink and monomer and other optionalcomponents are mixed and dispensed onto a polymer. In either instance,the monomer in the dispensed fluid can be polymerized, thus immobilizingthe ink therein at a defined locus.

Preferably, during printing, a printing device, such as an ink jetprinter, will dispense four different main colors (Black, Magenta, Cyanand Yellow) as discrete dots that correspond to one or more dispensationvolumes of the printing device that do not mix. The dots are depositedas any combination of the main colors to form a collage of discrete dotsof different main colors that, to the unaided human eye generally appearto be a color or pattern rather than a collage of discrete dots. Thus,what is formed is a matrix of individual color dots next to each otherwith a boundary between them.

Such a pattern under magnification may appear as:

-   -   OOOOOOOOO    -   OOOOOOOO    -   OOOOOOOOOO        Depending on the number of dots, their density and distribution        the unaided human eye would perceive different colors,        intensity, hue and brightness.

The ink used in available technology, such as pad transfer printing andpad transfer devices, is highly viscous, such as up to 40,000 cps and ispartially polymerized. Such inks do not run and forms a large discretedot on dispensation. Such printing results in a very unnaturalappearance due to the large, unmixed dots. In the present technology,the viscosity of the ink can be low, such as less than about 100 cps,and can be between about 1 cps and about 10 cps. This low viscosityallows the dots to blend, either on their own, or upon the exertion ofexternal forces, such as vibrational energy. In this instance, the dotsdo not remain discrete, but rather blend together, such as:

-   -   OOOOOOOO    -   OOOOOOO    -   OOOOOOOOO        The result being an image that is a color and pattern that is a        “non-dot” color matrix that has a highly realistic appearance to        the unaided human eye.

The printing device dispenses ink or mixtures of inks onto a polymer,such as a lens, that corresponds to the digitally encoded image. Morethan one digitally encoded image can be dispensed onto a polymer.Monomer in at least one ink can be appropriately polymerized such thatthe ink is immobilized on or within the polymer. This process can berepeated with the same or different digitally encoded image in the sameor different orientation.

In the alternative, the digitally encoded image can be printed on a padtransfer printing device where it is optionally polymerized. The printedimage can then be transferred to a polymer, such as a contact lens,using appropriate pad transfer printing devices such as they are knownin the art FIG. 4.

III Method of Making a Lens with a Degitally Encoded Image-II

The present invention includes a method of making an article ofmanufacture that includes a digitally encoded image and a polymer,including the steps of printing a digitally encoded image on acomposition comprising a polymer, and forming a lens from said polymer.

In this aspect of the present invention, the digitally encoded image isprinted on a polymer that does not form a lens using a printing device.The polymer with the digitally encoded image is then formed into a lensusing an appropriate method, such as, for example, fabrication,cast-molding, spin-casting or a combination thereof.

When the lens is made using fabrication, the polymer with the digitallyencoded image is formed into a lens using appropriate fabricationmethods, including, for example, stamping, grinding or trimming (see theFIG. 5). The lens can also be made using cast-molding and spin casting(see, for example, FIG. 6, FIG. 7A and FIG. 7B).

FIG. 7B depicts one preferred aspect of the present invention. A lensstructure is made using, for example, spin casting. Etching, burning orcutting processes, such as methods using chemical, mechanical or lasermethods, are used to create well(s) or indentations. These wells orindentations preferably are aligned at a locus that corresponds to theiris of an eye. A digitally encoded image is printed on the lens,preferably at the location of the wells or indentations. The ink canoptionally be polymerized or partially polymerized when monomers arepresent in the ink. A layer of polymer is then created on top of thisstructure to form a lens structure. Any appropriate polymerization ofthe structure thus formed or portions thereof can be accomplished usingappropriate methods.

In one instance, a digitally encoded image can be printed onto thesurface of a spin casting device, where the printed digitally encodedimage can be optionally polymerized or partially polymerized. A solutionincluding at least one monomer that can be polymerized to form a lens,such as a contact lens, can be dispensed on the printed digitallyencoded image and spin cast to form a lens. Preferably, the ink(s) usedto print the digitally encoded image include the same monomer(s) used tomake the lens, but that need not be the case. Preferably, the printeddigitally encoded image is non-polymerized or partially polymerized andcontacted with the solution including at least one monomer (preferablythe same monomer used in the ink(s)). The lens is formed byspin-casting, and the polymerization process completed. In that way, aself-adhesion bond or a polymer-polymer bond between the printeddigitally encoded image and the lens is made.

In another instance, a first solution including at least one monomer canbe polymerized or partially polymerized to form a lens, such as acontact lens, in a spin cast device. A digitally encoded image can beprinted on the exposed surface of the lens using a printing device andthe printed digitally encoded image optionally polymerized. A secondsolution including at least one monomer that can be polymerized to forma lens, such as a contact lens, is placed on top of the printeddigitally encoded image and is spin cast to form a lens. The secondsolution preferably is the same solution as the first solution.Preferably, the first solution is partially polymerized prior to theprinting of the digitally encoded image, wherein the printed digitallyencoded image includes the monomer of the first solution. This structureis optionally polymerized or partially polymerized. The second solutionpreferably includes the monomer of the first solution and the ink(s)used to make the digitally encoded image. Preferably, the firstsolution, the printed digitally encoded image and the second solutionform a partially polymerized structure, and the polymerization is thencompleted. In that way a polymer-polymer bond form between thepolymerized first solution and the polymerized printed digitally encodedimage or between the polymerized printed digitally encoded image and thepolymerized second solution. Preferably, such polymer-polymer bond formsbetween the polymerized first solution, the polymerized printeddigitally encoded image and the polymerized second solution.

In another instance, the present invention includes a polymeric surfacethat includes indentation structures, such as but not limited to groovesor wells that can be formed in the polymeric surface by a variety ofmethods, including casting and etching, cutting, drilling or burning,such as by laser etching, physical etching or chemical etching (see, forexample, FIG. 8A and FIG. 8B). Preferably, the indentation structuresare made using appropriate laser etching technologies, such as thosemade by Lumonics Inc.

The indentation structures can be provided at any locus at anyappropriate density of indentation structures on a surface, but arepreferably located in areas where pigmentation or printing is targeted,such as where a desired cosmetic effect is desired for contact lenses.Locations where printing is not desired or desirable can be providedsubstantially without such indentation structures such that printing canbe particularly directed or not directed to chosen locations.

The indentation structures can be of different sizes and shapes, but arepreferably relatively small such that one, a few or many droplets of inkcan be deposited into such indentation structures using appropriateprinting methods or devices (see, for example, FIG. 9). Preferably, oneor a few of the same color or different colors can be deposited in theindentation structures. In one aspect of the present invention, theindentation structures are partially filled or fully filled with inkduring printing processes. If the indentation structures areover-filled, then steps can be taken to remove excess ink, such as, forexample, blotting, scraping or machining, such as polishing, buffing orgrinding.

In a particularly preferred aspect of the present invention, the inkincludes at least one polymerizable monomer that can be polymerizedafter dispensation. If the indentation structures are not filled withsuch ink, then additional material, such as monomer with or without inkcan be dispensed onto the polymer. As in other aspects of the presentinvention, the skilled artisan has the choice of when and how the ink ormonomer can be polymerized. For example, in one preferred aspect of thepresent invention, the ink is dispensed into indentation structures suchthat the indentation structures are not filled. The ink is thenoptionally polymerized, and additional monomer is dispensed on thepolymer to fill or overfill the indentation structures. The monomer isthen polymerized, and the polymer is ready for final processing, if any.

Preferably, the indentation structures facilitate holding the dispensedink in a location such that a digitally encoded image is localized andheld in place. This aspect of the present invention is most appropriatefor inks that are of relatively low viscosity such that the ink does notrun due to the curvatures of printed surfaces, such as are present inlenses.

In one preferred aspect of the present invention, droplets of ink thatinclude a monomer are deposited on a surface, such as a polymer, thatincludes indentation structures. One or more droplets of the same ordifferent color are deposited in such indentation structures such thatdifferent combinations of colors, chroma, intensity and hues can belocalized in one or more indentation structures.

In another aspect of the present invention, a lens such as anon-hydrated lens or hydrated lens, such as a partially hydrated orfully hydrated lens, can be mounted, preferably centered, and masked ona fixture (see, for example FIG. 10). When hydrated, water on or in thelens can optionally be removed, such as by blotting. A hydrated lens canoptionally then be dehydrated, such as to partial or substantialdehydration, by appropriate methods such as by air, heat orcentrifugation. The lens can be printed or tinted using appropriatemethods such as those described herein. Preferably but optionally, thelens includes indentation structures such as those described herein.This process and device allow for the automation of printing processesand manufacture processes described herein.

The present invention also includes a method of making an article ofmanufacture that includes a digitally encoded image and a polymer,including the steps of printing a digitally encoded image on acomposition comprising at least one monomer, polymerizing said at leastone monomer to form at least one polymer, and forming a lens from saidat least one polymer.

The present invention includes a method of making an article ofmanufacture that includes a digitally encoded image and a polymer,including the steps of printing an image on at least one first surface,transferring said image to at least one second surface comprising amonomer or a polymer, and forming a lens from said second surface.

IV Digital Images

The present invention includes an article of manufacture, including: atleast one information storage medium, and at least one digital image,wherein the at least one digital image comprises at least a portion ofan image, such as, but not limited to, the iris of an eye. Theinformation storage medium can be any appropriate electronic storagemedium and is preferably in a machine readable format and preferablyassociated with a central processing unit. A plurality of digital imagescan be stored in a database. The invention is drawn not only todigitally encoded images, but also to the digitally encoded images whenprovided in a format, such as data, such as data in a patentable format.Thus, for example, the present invention encompasses a format such as amachine-readable format comprising data such as one or more digitallyencoded images of interest as determined or isolated according to thepresent invention.

For example, the invention includes data in any format, preferablyprovided in a medium of expression such as printed medium, perforatedmedium, magnetic medium, holographs, plastics, polymers or copolymerssuch as cyclo-olefin polymers. Such data can be provided on or in themedium of expression as an independent article of manufacture, such as adisk, tape or memory chip, or be provided as part of a machine, such asa computer, that is either processing or not processing the data, suchas part of memory or part of a program. The data can also be provided asat least a part of a database. Such database can be provided in anyformat, leaving the choice or selection of the particular format,language, code, selection of data, form of data or arrangement of datato the skilled artisan. Such data is useful, for example, for comparingsequences obtained by the present invention with known sequences toidentify novel sequences.

One aspect of the invention is a data processing system for storing andselecting at least a portion of data provided by the present invention.The data processing system is useful for a variety of purposes, forexample, for storing, sorting or arranging such data in, for example,database format, and for selecting such data based on a variety ofcriteria, such as colors, patterns, sources and the like. Such a dataprocessing system can include two or more of the following elements inany combination:

I. A computer processing system, such as a central processing unit(CPU). A storage medium or means for storing data, including at least aportion of the data of the present invention or at least a portion ofcompared data, such as a medium of expression, such as a magnetic mediumor polymeric medium;

II. A processing program or means for sorting or arranging data,including at least a portion of the data of the present invention,preferably in a database format, such as a database program or anappropriate portion thereof such as they are known in the art (forexample EXCEL or QUATROPRO);

III. A processing program or means for comparing data, including atleast a portion of the data of the present invention, which can resultin compared data, such as digital image comparing programs or anappropriate portion thereof;

IV. A processing program or means for analyzing at least a portion ofthe data of the present invention, compared data, or a portion thereof,particularly statistical analysis, such as programs for analyzingdigitally encoded images using statistical analysis programs or imagecomparing programs or an appropriate portion thereof as they are knownin the art;

V. A formatting processing program or means that can format an outputfrom the data processing system, such as data of the present inventionor a portion thereof or compared data or a portion thereof, such asdatabase management programs or word-processing programs, or appropriateportions thereof as they are known in the art; or

VI. An output program or means to output data, such as data of thepresent invention or a portion thereof or compared data or a portionthereof in a format useful to an end user, such as a human or anotherdata processing system, such as database management programs orword-processing programs or appropriate portions thereof as they areknown in the art. Such formats useful to an end user can be anyappropriate format in any appropriate form, such as in an appropriatelanguage or code in an appropriate medium of expression.

V Systems

The present invention also includes a system, including: an article ofmanufacture of the present invention and a printing device. The articleof manufacture includes at least one digitally encoded image, preferablyin the form of a database within a central processing unit. The centralprocessing unit preferably is linked to a printing device that includesappropriate software and hardware to direct the printing device to printa digitally encoded image, such as during the operation of a method ofthe present invention. The system can include additional components,such as devices for the manufacture of lens structures of the presentinvention. For example, the system of the present invention can includea lens manufacturing device, such as a spin casting device or a padtransfer device. Preferably, the central processing unit includeshardware and software that allows the central processing unit to directthe manufacture of a lens using at least one method of the presentinvention.

As a preferred embodiment of the present invention, a system of thepresent invention includes a first central processing unit thatoptionally includes an article of manufacture of the present invention,wherein the article of manufacture of the present invention can belocated on at least one second central processing unit separate indistance from the first central processing unit and is linked to theremainder of the system. The system preferably includes a printingdevice as described herein or known in the art that is capable ofprinting at least one digital image of the present invention. The systempreferably includes a lens manufacturing device, such as a spin-castdevice or a pad transfer device. In that regard, the system of thepresent invention includes dispensation and other hardware, software andreagents used to practice a method of the present invention. Preferably,the system is automated such that a user can select a digital image andthe first central processing unit directs and coordinates themanufacture of at least one lens by the remainder of the elements of thesystem, such as the printing device and a lens manufacture device.

VI Compositions of Matter Including Ink

The present invention also includes a composition of matter, includingat least one ink, dye, vat dye, particle, pigment, reactive dye or diazodye. The composition of matter also includes at least one of a binder,monomer, polymer, homopolymer, heteropolymer, copolymer, and initiator,UV initiator, thermal initiator, solvent, dispersant, anti-bacterialagent, anti-microbial agent, anti-fungal agent, disinfectant, thickener,humectant, non-kogating agent, anti-corrosion agent, antiseptic agent ornon-oxidizing agent. The indicated agents can be provided in anycombination and at concentrations or amounts appropriate for theindicated function.

The compositions of matter of the present invention do not include theinks set forth in U.S. Pat. No. 4,303,9214 to Young, issued Dec. 1,1981. In particular, the composition of matter of the present inventionare preferably water resistant after polymerization such that pigmentsin the ink substantially stay where they have been deposited by printingprocesses. In addition, the compositions of matter of the presentinvention are preferably swellable after polymerization, particularly insolvents, preferably water. In addition, the inks of the presentinvention, are preferably capable of chemically bonding, cross-linkingor otherwise binding with polymers or monomers on the surface beingprinted. For example, the ink of the present invention can includemonomers that can be polymerized with a polymer or monomer on thesurface being printed.

The composition of the present invention can be provided in a printingdevice, such as an ink jet printing device, a piezo printing device, athermal printing device, a laser printing device or a pad transferprinting device.

VII Method of Doing Business

The present invention also includes a method of doing business,including the steps of: obtaining a digital image from a person,database (such as a database of the present invention) or image andprinting said digital image to make at least one lens or a pair oflenses that includes the printed digital image. Preferably, the lens orlenses are made using a method of the present invention. Furthermore,the lens or lenses are preferably made using a system of the presentinvention.

In this aspect of the present invention, a customer selects an imagethat s/he would like as part of a lens. The image can be any image, suchas a fanciful image or any type, such as novelty images including swirlsand the like, or an image that is a high quality image of an iris, suchas from a human or animal. The image can be selected from a database,such as a database of digital images. Alternatively, the customer canidentify and select an image from a variety of sources, such as acollection of photographs of people or animals. Such collections can bein an appropriate storage medium, such as an electronic database or acollection or compilation of photographs or pictures. Alternatively, thecustomer can provide a selected image for use in the present method. Aselected non-digital image can be transformed into a digital image usingappropriate scanning technologies as they are known in the art. Suchscanned images can become part of a database of the present invention.The selection process can take place at virtually any location, such asat a vendor's or manufacturer's physical location or via computer, suchas via the Internet.

The digital image selected by the customer can then be conveyed to thevendor's or manufacturer's physical location via an appropriate method,such as through personal communication, phone communication,communication through printed materials such as order forms through themail, or through electronic media, such as through the Internet. Aselected image can be analyzed using appropriate software, such as imageanalysis and comparing software, for patterns, hue, chroma andintensity. The image can then be transformed into a signal for use by aprinting device such that the image is reproduced as to colors andpatterns by the printing device. The vendor notifies the manufacturer ofthe order and provides the manufacturer with the necessary information,such as the digital image. The vendor and manufacturer can be the sameor different person, company or entity and can be at the same ordifferent physical location. The manufacturer then manufactures the lensor lenses and delivers the manufactured lens or lenses to the vendor orcustomer by an acceptable method such as check, cash, credit, or creditcard. The vendor or manufacturer receives payment as appropriate.

The digital image can be printed by a printing device following a methodof the present invention or other method known in the art or laterdeveloped that results in the production of a lens, particularly acontact lens, of the present invention. Preferably, a printing devicethat utilizes at least two colors, at least three colors or at leastfour colors is used. This aspect of the present invention preferablyutilizes a system of the present invention.

VIII Use of Polymer Substrate Pre-Treatment Processes and Image ReceiverLayer

The present invention also includes an article of manufacture, includinga polymer substrate and a digitally encoded image made with ink, whereinthe polymer substrate forms a lens and is subjected to a pre-treatmentprocess that precedes the application of the digitally encoded image tothe polymer substrate. The pre-treatment process results in an enhancedimage quality of the digitally encoded image.

A polymer substrate, such as a lens, on which an image is to be printed,may be pre-treated prior to the printing process in order to improve thequality of the image, the quality of the printed polymer substrate, orboth. A suitable pre-treatment process may include one or more physicalor chemical modifications of the polymer substrate. For example, aphysical or chemical modification of the surface of the polymersubstrate may improve reproduction, resolution, durability, or realismof the image. Pre-treatment processes may modify the polymer substrateor polymer substrate surface, for example, by increasing or decreasingthe polymer substrate's wettability, porosity, or permeability.Pre-treatment processes may improve the polymer substrate's surfacemorphology, printability, stability, or durability. Formation of a lensfrom the polymer substrate may occur prior to, during, or after, one ormore pre-treatment processes.

Physical modifications may include, but are not limited to, etching,cutting, burning, heating, cooling, grinding, buffing, polishing,texturing, engraving, scribing, permeabilizing, and other mechanical ornon-mechanical treatments, which may roughen or smoothen the polymersubstrate's surface. Physical modifications may be made by any suitablemeans. In one example, a mechanical polisher can be used to polish,grind, or mill the polymer substrate's surface. In other examples, atool, such as a diamond tool, can be used to cut the surface of thelens, or the lens may be fabricated with a lathe. In another example, alaser can be used to smoothen the polymer substrate's surface, or, inone alternative, a laser can be used to add texture or pattern (such asindentations or wells) to the polymer substrate's surface.

Chemical modifications may include, but are not limited to, chemicalcleaning; chemical texture modifications (for example, etching,texturing, permeabilizing, smoothening, polishing, or combinationsthereof); chemical or electrochemical activation or creation of reactivegroups on or within the polymer substrate (for example, surfaceactivation or ionization by treatment with high voltage, flame, ozone,corona, plasma, or combinations thereof), chemical coating, andtreatment with acid, base, oxidizer, reducer, solvent, diluent, monomer,co-monomer, polymer, initiator, crosslinker, inhibitor, or otherchemicals including reactive or non-reactive components of the ink usedin printing the image. Non-limiting examples of chemical modificationsfollow. A surfactant or wetting agent can be applied to the polymersubstrate to improve wettability (for example, ethanol or isopropylalcohol may be applied by means of a swab or aerosol spray to a hydrogelcontact lens to improve the lens surface's wettability). The polymersubstrate can be impregnated or soaked in a chemical that changes thepolymer's degree of swelling (for example, a hydrogel contact lens maybe impregnated with methanol to swell the lens). The polymer substratecan be treated by plasma or by corona treatment in order to provide atemporary electrochemical modification of the surface. A hydrogelcontact lens can be coated with aziridine or with a primer to improvethe bonding between a reactive dye ink and the lens substrate.Carboxylic acid functional groups on the surface of a polymer substratecan be esterified with alcohols or other hydroxyl-bearing agents, withor without a catalyst. A corrosive agent can be used to etch the polymersubstrate (for example, hydrofluoric acid can be sprayed onto a hydrogelcontact lens to etch the surface).

An enhancement in image resolution and improvement to overall imagequality can be achieved by the use of an image receiver layer during theprinting process. The image receiver layer includes a chemical coatingthat is applied in a layer, such as a thin layer, to the surface of thepolymer substrate, which may form a lens. The polymer substrate can beporous, semi-porous, non-porous, or a combination thereof. Formation ofa lens from the polymer substrate may occur prior to, during, or after,application of the image receiver layer to the polymer substrate. Animage, such as a digitally encoded image, is printed, directly orindirectly (for example, directly by an ink jet printer) by transferringink onto or into the image receiver layer. Formation of a lens from thepolymer substrate may occur prior to, during, or after, printing of adigitally encoded image.

The image receiver layer serves to stabilize the ink by retaining theink in discrete droplets or “dots” in the desired location within theimage. Stabilizing the ink droplets can prevent excessive mixing orbleeding of the colors, for example, as may occur if the ink dropletswere allowed to remain wet directly on the surface of a hydrophilicpolymer substrate, or under humid conditions, such as those routinelyused during the fixing process. The ink's reactive components (such as apolymerizable monomer or a reactive dye) contact the polymer substratethrough the image receiver layer and, upon exposure to appropriateconditions, undergo a fixing reaction that fixes the reactive componentnon-transiently to the polymer substrate. The fixed reactive componentis non-transiently fixed to the polymer substrate in that the fixedreactive component is not substantially removable from the polymersubstrate by the normal post-fixation processes (such as lens hydrationand sterilization) or during normal use (such as normal wearing of acontact lens by a subject). The fixing reaction can include, forexample, covalent or non-covalent chemical bonding, cross-linking, orother bonding with the polymer substrate. The image receiver layerenhances the print quality by controlling the way in which the ink ispresented for fixation to the polymer substrate. The image receiverlayer retains the ink droplets in the desired position and preventsbleeding of the ink, but does not necessarily otherwise modify thefixing reaction of the ink's reactive components onto the polymersurface. In cases wherein the image receiver layer does modify thefixing reaction of the ink's reactive components onto the polymersurface, the modification is preferably an enhancement of the fixingreaction, for example, an increase in the efficiency, rate, or bondstrength of the fixing reaction.

The image receiver layer can be applied to a porous, semi-porous, ornon-porous polymer substrate such as, but not limited to,hydroxyethylmethacrylate (HEMA) homopolymers or copolymers,polymethylmethacrylate, glass, fluorosilicone acrylate, silicone,silicone acrylate, polystyrene, butylstyrene, alkylstyrene, glycidol(glycidyl) methacrylate, N,N-dimethylacrylamide, andpolyvinylpyrrolidone. Alternatively, the image receiver layer can beapplied to a prior layer on the polymer substrate. Such a prior layercan be, for example, one or more prior polymer layers, which may includethe same polymer or a different polymer as that included in the polymersubstrate. The prior layer can be a prior polymer layer that contains acoloring agent (for example, a dye or an opaque pigment, such astitanium dioxide). An image can be printed, directly or indirectly, bytransferring ink to the prior layer, whereby the image receiver layerholds the ink in place and prevents bleeding of the ink, thus enhancingthe image quality upon the prior layer (for example, by improving thefinal visibility of the fixed ink against an opaque pigment background).

The image receiver layer is applied in a thin layer, such as a layer ofbetween about 0.1 micrometers to about 200 micrometers, or between about0.1 micrometers to about 150 micrometers, or between about 0.1micrometers to about 100 micrometers, or between about 0.1 micrometersto about 50 micrometers, or between about 0.1 micrometer to about 20micrometers. Preferably, the image receiver layer is applied in a layerof between about 0.1 micrometer to about 20 micrometers. The imagereceiver layer can cover the entire area or only partial areas of thepolymer substrate, preferably in areas wherein an image is to beprinted, such as, but not limited to, a circular or annular area whereinan image of an iris is to be printed on a contact lens. The imagereceiver layer can be applied to the polymer substrate by any suitablemeans, such as, but not limited to, direct coating (for example, byapplication using a brush, swab, pipette, or sponge), application ofdroplets or microdroplets (for example, by application using an aerosolspray or an ink jet printer), soaking, impregnation, spin coating, dipcoating, curtain coating, or pad printing.

The image receiver layer composition preferably has a viscosity and asurface tension suitable for the chosen method of application andcompatible with the chosen reactive dye inks. One example of an imagereceiver layer composition suitable for application by direct coating(for example, by means of a pipette) or by soaking is a solution of 10%ViviPrint™ 121 (a neutralizedpoly(vinylpyrrolidone/dimethylamino-propylmethacrylamide) copolymer, CASnumber 175893-71-1, supplied as a 10% in water composition with aviscosity of between about 7 to about 23 centipoises at about 25 degreesCelsius, a nominal molecular weight of about 1.05×10⁶ grams per mole,and a glass transition temperature (Tg) of about 184 degrees Celsius)(product ID 72417D, International Specialty Products, 1361 Alps Road,Wayne, N.J. 07470) in industrial methylated spirits (IMS) having aviscosity of about 5.18 centipoises and a surface tension of about 25.5dynes per centimeter. Another example of an image receiver layercomposition suitable for application by direct coating or soaking is asolution of 10% ViviPrint™ 121 in water having a viscosity of about 30.5centipoises and a surface tension of about 40.0 dynes per centimeter. Athird example of an image receiver layer composition suitable forapplication by direct coating or soaking is a solution of 10% ViviPrint™121 in water containing 3.6% sodium hydroxide having a viscosity ofabout 4.54 centipoises and a surface tension of about 35.5 dynes percentimeter. A fourth example of an image receiver layer compositionsuitable for application by direct coating or soaking is a solution of5.3% PVP K30 (polyvinylpyrrolidone supplied as a hygroscopic, amorphouswhite powder with a viscosity (for a 5% solution) of about 3 centipoisesat about 25 degrees Celsius, a nominal molecular weight of about 60×10³grams per mole, and a glass transition temperature (Tg) of about 163degrees Celsius) (International Specialty Products, Wayne, N.J.) inwater containing 5.3% sodium phosphate having a viscosity of about 3.37centipoises and a surface tension of about 55.5 dynes per centimeter.Another source for PVP K30 (also known as Povidone or PVP, CAS number9003-39-8, polyvinylpyrrolidone with an average molecular weight ofabout 29,000) is catalogue number 23,425-7 (Sigma-Aldrich 2003–2004catalogue, P. O Box 2060, Milwaukee, Wis.). These above examples andsimilar compositions can also be applied in microdroplets, for example,by ink jet printing or as an aerosol. Image receiver layer compositionswith viscosities greater than about 20 centipoises may need a heatedprint head to reduce the composition viscosity to a range suitable forcurrent ink jet technologies (between about 15 to about 20 centipoises).In another example, an image layer composition suitable for applicationby pad transfer printing is preferably formulated with a viscosity ofbetween about 5000 to about 50,000 centipoises. After application, theimage receiver layer optionally undergoes a drying process, for exampleby air-drying, or by exposure to low humidity conditions, or by exposureto gentle heat (such as from room temperature to about 90 degreesCelsius), in order to increase its absorbency for ink.

The image receiver layer preferably is compatible with the relativehydrophilicity or hydrophobicity of the solvent or other carriercomponents with which the ink is formulated. The image receiver layerpreferably is capable of absorbing the solvent or other carriercomponents (such as, but not limited to, organic or aqueous solvents orco-solvents, humectants, surfactants, or diluents) with which the ink isformulated, and in this manner reduces migration or bleeding of the ink.Preferably, the image receiving layer is highly absorbent, able toabsorb at least 5%, and more preferably at least 10%, of the imagereceiving layer's dry weight of the ink's solvent or other carriercompounds. Non-limiting examples of synthetic materials that may besuited to an image receiver layer include highly absorbent polymers suchas polyvinylpyrrolidones, polyacrylamides, polyacrylates, and theirhomopolymers and copolymers (for example, apoly(vinylpyrrolidone/dimethylaminopropylmethacrylamide) copolymer).Examples of naturally derived materials that may be suited to an imagereceiver layer include proteinaceous materials such as, but not limitedto, gelatin, collagen, albumin (for example, egg albumin or serumalbumin), casein, and plant gluten proteins, and carbohydrate basedmaterials such as cellulose or starch; synthetic or semi-synthetichomologues of such naturally derived materials may also be suitable. Forexample, where the ink to be used is water based, the image receiverlayer is preferably compatible with water and capable of high waterabsorbency without itself becoming dissolved; an example of an imagereceiver layer that is compatible with a water based ink ispolyvinylpyrrolidone, which can have a water absorptivity of betweenabout 5% to about 35% water, or about 17% water at a relative humidityof 60% and at 20 degrees Celsius.

The image receiver layer preferably also functions to attract orassociate with the ink colorants (such as reactive components) and thushold these colorants in place and prevent bleeding. Preferably, thisattraction or association should not be so strong as to inhibit transferof the colorant from and through the image receiver layer to the polymersubstrate for fixation. For example, polyvinylpyrrolidone ischaracterized by high polarity and an ability to hydrogen bond withactive hydrogen donors (such as phenols or carboxylic acids) or anioniccompounds, which may aid in attracting or associating with the inkcolorants.

The composition of the image receiver layer is such that it will notsubstantially adversely react with the reactive components used in theink, and thus does not substantially inhibit the fixing reaction of thereactive component onto the polymer substrate. For example, an imagereceiver layer, suitable for use with an ink that is fixed by a reactioninvolving displacement of a leaving group, preferably does not itselfcontain such displaceable leaving groups. In another example, an imagereceiver layer, suitable for use with an ink including components thatreact with reactive hydroxyl, amine, or thiol groups of the polymersubstrate, preferably does not itself contain reactive hydroxyl, amine,or thiol groups. In another example, an image receiver layer, suitablefor use with an ink that is fixed by a reaction involving base-catalysis(such as base-catalyzed opening of an epoxide ring, base-catalyzedsolvolysis of esters or ethers, or base-catalyzed elimination),preferably does not itself contain such base-reactive groups. The imagereceiver layer preferably also does not substantially adversely reactwith (for example, substantially corrode or weaken) the polymersubstrate.

The image receiver layer can form a discrete layer on the polymersubstrate or can penetrate, wholly or partially, the polymer substrate.The image receiver layer can optionally have the ability to swell thepolymer substrate sufficiently to aid in the transfer of the ink'sreactive component onto or into the polymer substrate. Preferably, theimage receiver layer should not swell the polymer substrate to anundesirable extent (for example, where oversaturation of the polymersubstrate by the image receiver layer inhibits ink transfer or inkfixation, or where swelling of the polymer substrate causes distortionof the lens shape). One example of an image receiver layer compositionthat is capable of swelling a polymer substrate is a ViviPrint™ 121 orPVP K30 composition that includes a short chain alkyl alcohol (such as,but not limited to, methanol, ethanol, n-propanol, or iso-propanol), tobe used with a hydroxyethylmethacrylate-based (HEMA-based) polymersubstrate, such as a HEMA-based soft contact lens.

The image receiver layer may be non-transiently incorporated into oronto the polymer substrate, or may be temporary. A non-transient imagereceiver layer is one that is not substantially removed from the polymersubstrate by the normal post-fixation treatment processes, such as lenshydration and sterilization. A non-transient image receiver layer caninclude an image receiver layer that is non-transiently bonded to thepolymer substrate, or an image receiver layer that is non-transientlyincorporated within the polymer substrate (for example, copolymerizedwithin the polymer substrate). A temporary image receiver layer ispreferably substantially or completely removable from the polymersubstrate, for example, by washing with warm or hot water, exposure tosteam, or by washing with base solution. More preferably, a temporaryimage receiver layer is conveniently removable during the normalpost-fixation treatment processes. For example, in the manufacture ofHEMA-based soft contact lenses, lenses may be hydrated by placing themin an aqueous solution of 0.5% sodium bicarbonate containing 0.005%surfactant, heating the solution to about 50 degrees Celsius, andmaintaining the temperature between about 50 to about 60 degrees Celsiusfor about 30 minutes. HEMA-based soft contact lenses may be sterilizedby placing in vials containing a 0.9% aqueous sodium chloride solutioncontaining 0.015% sodium bicarbonate and 0.005% surfactant, capping andcrimping the vials, placing the vials in an autoclave, andsteam-sterilizing the lenses for about 25 minutes at about 121 degreesCelsius.

Use of the image receiver layer is preferably compatible with othertreatments of the polymer substrate that occur prior to, during, orafter printing of the image. For example, it may be desirable to treatthe polymer substrate with an activating substance, such as, but notlimited to, a base (for example, sodium hydroxide, sodium carbonate, orsodium phosphate) in order to activate the polymer substrate or tocatalyze the fixing reaction between the polymer substrate and thereactive components of the ink. In such a case, the image receiver layeris preferably compatible with the base treatment and will not adverselyreact with the reactive components used in the ink. Preferably, theimage receiver layer may be applied prior to, after, or simultaneously(for example, as a single solution containing both the image receiverlayer composition and the base treatment composition) with the basetreatment. An example of a single solution containing both the imagereceiver layer composition and the base treatment composition is PVP K30combined at up to 5% with a 5% solution of sodium phosphate aqueoussolution. Another example of base compatibility is ViviPrint™ 121, whichmay be added to sodium hydroxide solutions (although not to sodiumphosphate solutions).

Optionally, the image receiver layer composition may be added to an ink,either a stand-alone ink to apply the image receiver layer prior toprinting with an ink containing a reactive dye, or an ink containing areactive dye. The viscosity of such an image receiver layer/inkcombination must be within the range suitable to the requirements of theprinting process, for example, within an acceptable viscosity range foran ink jet print head where the image is applied by ink jet printing.

IX Method of Using Pre-Treatment Processes and Image Receiver Layer inMaking a Lens

The present invention also includes a method of making an article ofmanufacture that includes a polymer substrate and a digitally encodedimage made with ink, wherein the polymer substrate forms a lens,including subjecting the polymer substrate to a pre-treatment processthat precedes the application of the digitally encoded image to thepolymer substrate. The pre-treatment process results in an enhancedimage quality of the digitally encoded image.

The method may include pretreating a polymer substrate, such as a lens,on which an image is to be printed, prior to the printing process inorder to improve the quality of the image, the quality of the printedpolymer substrate, or both. A suitable pre-treatment process may includeone or more physical or chemical modifications of the polymer substrate.Formation of a lens from the polymer substrate may occur prior to,during, or after, one or more pre-treatment processes. Physicalmodifications may include, but are not limited to, etching, cutting,burning, heating, cooling, grinding, buffing, polishing, texturing,engraving, scribing, permeabilizing, and other mechanical ornon-mechanical treatments, which may roughen or smoothen the polymersubstrate's surface. Physical modifications may be made by any suitablemeans. Chemical modifications may include, but are not limited to,chemical cleaning; chemical texture modifications (for example, etching,texturing, permeabilizing, smoothening, polishing, or combinationsthereof); chemical or electrochemical activation or creation of reactivegroups on or within the polymer substrate (for example, surfaceactivation or ionization by treatment with high voltage, flame, ozone,corona, plasma, or combinations thereof), chemical coating, andtreatment with acid, base, oxidizer, reducer, solvent, diluent, monomer,co-monomer, polymer, initiator, crosslinker, inhibitor, or otherchemicals including reactive or non-reactive components of the ink usedin printing the image.

The method may include the use of an image receiver layer during theprinting process to enhance image resolution and improve overall imagequality. The image receiver layer includes a chemical coating that isapplied in a layer, such as a thin layer, to the surface of the polymersubstrate, which may form a lens. Formation of a lens from the polymersubstrate may occur prior to, during, or after, application of the imagereceiver layer to the polymer substrate. The polymer substrate can beporous, semi-porous, non-porous, or a combination thereof. An image,such as a digitally encoded image, is printed, directly or indirectly(for example, directly by an ink jet printer) by transferring ink ontoor into the image receiver layer. Formation of a lens from the polymersubstrate may occur prior to, during, or after, printing of a digitallyencoded image.

The image receiver layer serves to stabilize the ink by retaining theink in discrete droplets or “dots” in the desired location within theimage. The ink's reactive components (such as a polymerizable monomer ora reactive dye) contact the polymer substrate through the image receiverlayer and, upon exposure to appropriate conditions, undergo a fixingreaction that fixes the reactive component non-transiently to thepolymer substrate. The fixed reactive component is non-transiently fixedto the polymer substrate in that the fixed reactive component is notsubstantially removable from the polymer substrate by the normalpost-fixation processes (such as lens hydration and sterilization) orduring normal use (such as normal wearing of a contact lens by asubject). The image receiver layer enhances the print quality bycontrolling the way in which the ink is presented for fixation to thepolymer substrate. The image receiver layer retains the ink droplets inthe desired position and prevents bleeding of the ink, but does notnecessarily otherwise modify the fixing reaction of the ink's reactivecomponents onto the polymer surface.

The image receiver layer can be applied to a porous, semi-porous, ornon-porous polymer substrate such as, but not limited to,hydroxyethylmethacrylate (HEMA) homopolymers or copolymers,polymethylmethacrylate, glass, fluorosilicone acrylate, silicone,silicone acrylate, polystyrene, butylstyrene, alkylstyrene,glycidol(glycidyl)methacrylate, N,N-dimethylacrylamide, andpolyvinylpyrrolidone. Alternatively, the image receiver layer can beapplied to a prior layer on the polymer substrate. Such a prior layercan be, for example, one or more prior polymer layers, which may includethe same polymer or a different polymer as that included in the polymersubstrate. The prior layer can be a prior polymer layer that contains acoloring agent (for example, a dye or an opaque pigment, such astitanium dioxide). An image can be printed, directly or indirectly, bytransferring ink to the prior layer, whereby the image receiver layerholds the ink in place and prevents bleeding of the ink, thus enhancingthe image quality upon the prior layer.

The image receiver layer is applied in a thin layer, such as a layer ofbetween about 0.1 micrometers to about 200 micrometers, or between about0.1 micrometers to about 150 micrometers, or between about 0.1micrometers to about 100 micrometers, or between about 0.1 micrometersto about 50 micrometers, or between about 0.1 micrometer to about 20micrometers. Preferably, the image receiver layer is applied in a layerof between about 0.1 micrometer to about 20 micrometers. The imagereceiver layer can cover the entire area or only partial areas of thepolymer substrate, preferably in areas wherein an image is to beprinted, such as, but not limited to, a circular or annular area whereinan image of an iris is to be printed on a contact lens. The imagereceiver layer can be applied to the polymer substrate by any suitablemeans, such as, but not limited to, direct coating (for example, byapplication using a brush, swab, pipette, or sponge), application ofdroplets or microdroplets (for example, by application using an aerosolspray or an ink jet printer), soaking, impregnation, spin coating, dipcoating, curtain coating, or pad printing.

The image receiver layer composition preferably has a viscosity and asurface tension suitable for the chosen method of application andcompatible with the chosen reactive dye inks. For example, imagereceiver layer compositions with a viscosity of between about 15 toabout 20 centipoises at room temperature can also be applied inmicrodroplets at room temperature, for example, by ink jet printing oras an aerosol. Image receiver layer compositions with viscositiesgreater than about 20 centipoises may need a heated print head to reducethe composition viscosity to a range suitable for current ink jettechnologies (between about 15 to about 20 centipoises). In anotherexample, an image layer composition suitable for application by padtransfer printing is preferably formulated with a viscosity of betweenabout 5000 to about 50,000 centipoises. After application, the imagereceiver layer optionally undergoes a drying process, for example byair-drying, or by exposure to low humidity conditions, or by exposure togentle heat (such as from room temperature to about 90 degrees Celsius),in order to increase its absorbency for ink.

The image receiver layer preferably is compatible with the relativehydrophilicity or hydrophobicity of the solvent or other carriercomponents with which the ink is formulated. The image receiver layerpreferably is capable of absorbing the solvent or other carriercomponents with which the ink is formulated, and in this manner reducesmigration or bleeding of the ink. Preferably, the image receiving layeris highly absorbent, able to absorb at least 5%, and more preferably atleast 10%, of the image receiving layer's dry weight of the ink'ssolvent or other carrier compounds. Non-limiting examples of syntheticmaterials that may be suited to an image receiver layer include highlyabsorbent polymers such as polyvinylpyrrolidones, polyacrylamides,polyacrylates, and their homopolymers and copolymers (for example, apoly(vinylpyrrolidone/dimethylaminopropylmethacrylamide) copolymer).Examples of naturally derived materials that may be suited to an imagereceiver layer include proteinaceous materials such as, but not limitedto, gelatin, collagen, albumin (for example, egg albumin or serumalbumin), casein, and plant gluten proteins, and carbohydrate basedmaterials such as cellulose or starch; synthetic or semi-synthetichomologues of such naturally derived materials may also be suitable.

The image receiver layer preferably also functions to attract orassociate with the ink colorants (such as reactive components) and thushold these colorants in place and prevent bleeding. Preferably, thisattraction or association should not be so strong as to inhibit transferof the colorant from and through the image receiver layer to the polymersubstrate for fixation.

The composition of the image receiver layer is such that it will notsubstantially adversely react with the reactive components used in theink, and thus does not substantially inhibit the fixing reaction of thereactive component onto the polymer substrate. The image receiver layerpreferably also does not substantially adversely react with (forexample, substantially corrode or weaken) the polymer substrate.

The image receiver layer can form a discrete layer on the polymersubstrate or can penetrate, wholly or partially, the polymer substrate.The image receiver layer can optionally have the ability to swell thepolymer substrate sufficiently to aid in the transfer of the ink'sreactive component onto or into the polymer substrate. Preferably, theimage receiver layer should not swell the polymer substrate to anundesirable extent.

The image receiver layer may be non-transiently incorporated into oronto the polymer substrate, or may be temporary. A non-transient imagereceiver layer is one that is not substantially removed from the polymersubstrate by the normal post-fixation treatment processes, such as lenshydration and sterilization. A non-transient image receiver layer caninclude an image receiver layer that is non-transiently bonded to thepolymer substrate, or an image receiver layer that is non-transientlyincorporated within the polymer substrate (for example, copolymerizedwithin the polymer substrate). A temporary image receiver layer ispreferably substantially or completely removable from the polymersubstrate, for example, by washing with warm or hot water, exposure tosteam, or by washing with base solution. More preferably, a temporaryimage receiver layer is conveniently removable during the normalpost-fixation treatment processes.

Use of the image receiver layer is preferably compatible with othertreatments of the polymer substrate that occur prior to, during, orafter printing of the image. For example, it may be desirable to treatthe polymer substrate with an activating substance, such as, but notlimited to, a base (for example, sodium hydroxide, sodium carbonate, orsodium phosphate) in order to activate the polymer substrate or tocatalyze the fixing reaction between the polymer substrate and thereactive components of the ink. In such a case, the image receiver layeris preferably compatible with the base treatment and will not adverselyreact with the reactive components used in the ink. Preferably, theimage receiver layer may be applied prior to, after, or simultaneously(for example, as a single solution containing both the image receiverlayer composition and the base treatment composition) with the basetreatment.

Optionally, the image receiver layer composition may be added to an ink,either a stand-alone ink to apply the image receiver layer prior toprinting with an ink containing a reactive dye, or an ink containing areactive dye. The viscosity of such an image receiver layer/inkcombination must be within the range suitable to the requirements of theprinting process, for example, within an acceptable viscosity range foran ink jet print head where the image is applied by ink jet printing.

X Separation of Ink Reactive Components

The present invention also includes an article of manufacture, includinga polymer substrate and a digitally encoded image made with ink thatincludes reactive components, wherein the polymer substrate forms a lensand wherein the digitally encoded image is applied to the polymersubstrate by ink jet printing. Each reactive component is stored in anink jet printer cartridge. The reactive components may be stored inseparate ink jet printer cartridges.

When using an ink that includes one or more reactive components, it isgenerally undesirable for such a reactive component to decrease theink's stability or shelf-life. For example, an ink that includespolymerizable monomers or polymers (such as hydroxyethylmethacrylate) orcrosslinking agents (such as hexamethyldiisocyanate) in its formulationmay, when stored over time, undergo polymerization or crosslinking,which is undesirable during storage. One solution to this is tocompartmentalize the reactive component or components and thus retard orprevent such undesirable reactions from occurring. Suchcompartmentalization would require formulation of the separatecomponents in such a manner as to ensure no undesirable side reactions(for example, side reactions between a crosslinking agent and apolymer). For example, it may be desirable to separately store thepolymerization initiator from the other components of a polymerizationreaction (such as polymerizable monomers and crosslinking agents). Wherethe printing process uses an ink jet printer, the reactive componentsmay be stored in separate or individual cartridges, thereby increasingthe stability and shelf-life of the ink. The reactive components as wellas the other components of the ink may then be applied as required tothe substrate on which the image is to be printed. For example,aziridine may be formulated with a pigment and stored in one cartridge,while suitably formulated methacrylic acid may be stored in a separatecartridge, thus increasing the shelf life of both formulations relativeto a single formulation stored in a single cartridge. The twoformulations may be ink jetted separately and sequentially, in order forthe polymerization reaction to begin only after ink jet application ofboth formulations to the same spot.

EXAMPLES Example 1 Preparation of Inks

This example provides ink compositions used to make lenses that includea digitally encoded image. Four ink preparations are preferred for usein printing devices, although more or less can be used.

The ink preparations include a base ink formulation that include thefollowing: monomer (HEMA), initiator (BME), crosslinker (EGDMA), pigment#1, diluent (glycerine), solvent (isopropanol), optional pigment #2(titanium oxide), dispersant (polyvinyl alcohol), humectant (ethyleneglycol), co-monomer (methacrylic acid), inhibitor (MEHQ), antikogatingagent (methyl propanediol), and antioxidant (alkylated hydroquinone).The concentration of these constituents are as appropriate for making alens of desired characteristics and physical properties. Pigment #1 canbe any ink or combination of inks to provide a desired color. Thepreferred colors for four ink formulations are A1: Black; A2: Magenta,A3: Yellow and A4: Cyan. Appropriate inks for A1, A2, A3, and A4 aredescribed in U.S. Pat. No. 5,176,745, U.S. Pat. No. 4,889,520, U.S. Pat.No. 5,658,376, U.S. Pat. No. 4,793,264, U.S. Pat. No. 5,389,132, U.S.Pat. No. 5,271,765, U.S. Pat. No. 5,062,892 and U.S. Pat. No. 5,372,852.

A preferred monomer mixture for making clear lenses is designate A5, andhas the following formulation: monomer (HEMA), monomer (EOEMA), monomer(MAA), crosslinker (EGDMA), initiator (Vazo-64), inhibitor (MEHQ) anddiluent (glycerine). The concentration of these constituents are asappropriate for making a lens of desired characteristics and physicalproperties.

When inks are used in jet printing devices, the ink is preferably waterbased or monomer based (U.S. Pat. No. 5,658,376). The ink is preferablysoluble in water and an organic solvent and preferably includes adisperse dye or pigment. A water soluble polymer such as polyvinylalcohol and a dispersant such as polyvinylpyrrolidone are preferred. Asurfactant is preferably provided, such as polyoxyethylene alkyl etheror polyoxyethylene alkylphenyl ether having an aminic acid group. Theink preferably includes a surfactant, such as between about 0.3% andabout 1% by weight. The ink preferably includes an antiseptic agent suchas Proxel (Zeneca, U.K.). The ink preferably has a pH of between about 7and about 10 and a viscosity at about 25 C of between about 2 mPas andabout 6 mPas. Antioxidants, such as low corrosion or antioxidant agents,such as alkylated hydroquinone can also be included, preferably betweenabout 0.1% and about 0.5% by weight (U.S. Pat. No. 5,389,132). An inkcan also include a humectant such as 1,3-dioxane-5,5-dimethanol,2-methyl-1,3-propane diol, ethylene glycol or diethylene glycol. Whenused in printing, the driving frequency is preferably between about 3kHz and about 8 kHz (see generally, U.S. Pat. No. 5,658,376). Preferredink properties include a surface tension of between about 20 dynes/cmand about 70 dynes/cm and a viscosity between about 1.0 cp and about 2.0cp (U.S. Pat. No. 5,271,765).

Example 2 Printing Methodologies—Surfaces and Laminates

This example, as depicted in FIG. 1 and FIG. 11, provides a methodologyfor printing digitally encoded images. An image, such as of an iris, isscanned into a digital form using appropriate hardware and software toprovide a digitally encoded image. The digitally encoded image is storedin an appropriate storage medium, such as an electronic medium, such asin a database. A selected image is sent via an electronic signal to aprinting device, such as an inkjet printing device, a bubble jetprinting device or a laser printing device, through a processing unit.The printing device preferably includes ink formulations A1, A2, A3 andA4 in separate compartments, such as in a printing cassette (FormulationA6), and optionally formulation A5 in a separate compartment or in aseparate cassette. The printing device, under the direction of aprocessing unit, prints the digitally encoded image by mixing anddispensing, or dispensing individually, the inks of formulation A6 ontoa surface, such as a polymerized polymer, a partially polymerizedpolymer or an unpolymerized polymer. After a printing step or other timeduring the manufacture process, the structure can be subjected toenergy, such as vibrational energy, that can smear the printed digitalimage, particularly when in an unpolymerized or partially polymerizedstate, such that the resulting printed digital image has a naturalappearance. This process can be repeated a plurality of times using thesame or different digitally encoded image. The surface can be maintainedin the same orientation or rotated between printing steps. The printeddigitally encoded image can be polymerized or partially polymerizedafter each printing step or after all printing steps are completed.

In the alternative, as depicted in FIG. 12 a digitally encoded image canbe printed on a structure designed to transfer a printed digitallyencoded image to a surface. Such structures known in the art include padtransfer devices. The digitally encoded image can be printed onto thestructure and polymerized or partially polymerized prior to the printeddigitally encoded image being transferred to a surface.

The surface that the digitally encoded surface is printed upon, ortransferred to, can be partially polymerized or fully polymerized, andcan be rough or smooth. Roughened surfaces are obtained by methods knownin the art, such as etching, laser cutting or burning, grinding orcutting. The surfaces can be made by appropriate methods, such as bycast molding, spin casting lathe fabrication or laser fabrication.

Laminate structures that include printed digitally encoded images can bemade by forming a surface with printed digitally encoded image on suchsurface. Additional monomer, such as formulation A5, can be placed onthe printed digitally encoded image and polymerized to form a laminatestructure that includes a first polymer layer (preferably clear), aprinted digitally encoded image, and a second polymer layer (preferablyclear). In making these laminate structures, the first polymer layer canbe partially or fully polymerized prior to printing of the digitallyencoded image. This structure in turn can be partially or fullypolymerized. The monomer for the second polymer layer is then dispensed,and this structure is then partially or fully polymerized (see, forexample, FIG. 2 and FIG. 13).

Example 3 Printing Methods—within a Well or Indentation on a Surface

This example, as depicted in FIG. 14 provides methods of making lensesthat include a digitally encoded image, wherein the digitally encodedimage is provided in a well structure(s) or an indentation(s). In thisaspect of the present invention, a structure including a surface offully polymerized or partially polymerized polymer is provided. A wellor indentation is created on the structure that corresponds at least inpart to the size and shape of the digitally encoded image to be printed.The well can be larger in size or of a different shape than thedigitally encoded image to be printed. The methods descried in Example 2are used to print the digitally encoded image on the surface of thewell. A laminate structure within the well can also be made followingthe methods described in Example 2.

Example 4 Finishing of Lenses

The structure resulting for these methods can be finished usingsecondary operations known in the art as they are needed, such as, forexample, cutting, grinding, edging, polishing or the like to form a lensof desired optical, cosmetic or functional quality or characteristics.For soft contact lenses, the dry lenses may be hydrated usingconventional methods to form a finished product. The finished lenses canbe packaged in any appropriate packaging as they are known in the art,such as vials, tubes, blisters or other structures. The packaging caninclude appropriate solutions and instructions for use or description ofthe product and its care.

Example 5 Polyfunctional Aziridine as a Crosslinker

The present invention provides additional bonding agents to improveadhesion of inks such as pigments to polymers, such as lenses. Thisexample provides improved adhesion of pigments to a polymer lens byusing a bonding agent that is believed to form a cross linked network.The crosslinked network is believed to be formed by exposing a polymerhaving a carboxyl group with about one percent to about five percent,preferably two percent, of a compound containing protonated aziridinegroups for example the polyfunctional aziridine crosslinker IONAC®PFAZ®-322 supplied by Sybron Chemicals (Birmingham, N.J.) (See, forexample, Sybron Chemicals Inc. product sheet for IONAC→PFAZ→322Polyfunctional Aziridine, which is incorporated by reference herein;IONAC® PFAZ®-322 is now supplied by Bayer·Corporation, Pittsburgh, Pa.)Reactions that protonate aziridine rings is believed to allow bindingbetween the protonated aziridine group and an oxygen within a carboxylgroup thereby crosslinking the polymer and enabling stabilization oflocalization of a dye such as a pigmented dyes. Typically, activehydrogens eligible to participate in cross linking with aziridineinclude: carboxyl, hydroxyl, primary or secondary amine, primary orsecondary amide and thiol or mercaptan. Not intending to be limited to amode of action, the resulting crosslinked network may entrap the dyesuch as a pigmented dye.

The purpose of this example is to evaluate the mechanical bonding of anink to a polymer and establishes the stabilization of the location of apigmented dye in a polymer. Various formulations used in these examplesare provided as follows:

Reagents

Cyan ink, Formula TD 70A Materials Percent Range Cyan dispersion X1780220 10–30 White dispersion X6985-185 7  5–15 30% Elvacite 2008 in EBAcetate 9  5–15 30% Epon 2004 in EB Acetate 9  5–15 Cyclohexanone 7 3–10 EB acetate 47.2 25–50 BYK UV 3500 0.8 0.1–2   Total 100

Cyan dispersion X17802 Material Percent Range Diacetone alcohol 20.7710–30 50% DM55 resin in DAA 20.77 10–30 Efka 47 35.61 20–50 Solsperse5000 2.08 0.5–10  Irgalite Blue LGE 20.77 10–30 Total 100 DAA Diacetonealcohol solvent DM55 Acrylic resin made by Rhom & Hass. Resin is used inthe Dispersion to provide surface for the pigment and dispersantparticles to anchor. Resin also increase viscosity needed in Millingprocess, and wet the pigment. Efka 47 A polymeric dispersant withpigment affinity groups, made by Lubrizol. The main purpose ofdispersant is to disperse the pigment, separate them so they will notagglomerate together. Another purpose is to wet the pigment. Solsperse Asynergist made by Avecia (former Zeneca). 5000 Synergist is used in aPigment dispersion to help stabilize the pigment. It serves as a bridgeto connect between the pigment particle and the main polymericDispersant, in this case Efka 47. Irgalite A phthalocyanine blue 15:3pigment, made by Ciba Blue LGE Geigy, Inc. This Product is no longercommercially available. A substitution pigment is Irgalite Blue NGA,also a phthalocyanine 15:3 pigment. BYK UV A surface additive made byBYK Chemie. This additive 3500 is to help the ink wet the non poroussubstrates such as glass, vinyl, metal, plastic, PVC, and the like andit helps the ink to flow well inside the print head.

White Pigment Dispersion X6985-185 Material Percent Range Diacetonealcohol 21.41 10–30 50% DM55 resin in Diacetone Alcohol 35.66 20–50Disperbyk 110 4.13  1–10 White pigment Tioxide Comet 300 38.80 30–60Total 100 Disperbyk A dispersing agent copolymer made by BYK Chemie. 110Tioxide A white pigment, chemical index White 6, made by Comet 300TIOXIDE company. 30% Elvacite 2008 in Ethylene Glycol Butyl EtherAcetate (EB Acetate) Ethylene Glycol butyl ether acetate  70% Elvacite2008 dry resin  30% Total 100 Elvacite 2008 Acrylic resin supplied byIneo Acrylic (Cordova, TN) 30% Epon 2004 in Ethylene Glycol butyl etherAcetate (EB Acetate) EB Acetate  70% Epon 2004 resin  30% Total 100%Epon 2004 resin An Epoxy resin made by Shell Chemical. Other ReagentsBX-HEMA A mixture of about 97.8% HEMA, about 0.7% EGDMA LLT and about1.5% MAA. Ionac A bonding agent, Aziridine type, previously supplied byPFAZ-322 Sybron, Birmingham, currently supplied by Bayer, Pittsburg PAas PFAZ-322.Experiment

Control Formulation A:

1. TD-70A Cyan ink

Experimental Formulation B:

1. TD-70A Cyan ink

2. Ionic® PFAZ®-322 (Sybron Chemicals, Inc., Birmingham, N.J.) 2%

Experimental Formulation C:

1. TD-70A Cyan ink

2. Ionac® PFAZ®-322 (Sybron Chemicals, Inc., Birmingham, N.J.) 2%

3. BX-HEMA LLT 40%

Each formulation was mixed and ink jet printed on HEMA lenses using aBudjet IV printer (Fas-co Encoder, Chandler, Ariz.). in addition,thermal initiators and/or UV initiators of polymerization arecontemplated for these formulations to improve adhesion and/or time forpolymerization. Digitally encoded images of letters were ink jet printedonto the HEMA lenses. The lenses were cured at 70 degrees Celsius for 16hours. The lenses were then hydrated and extracted in distilled water at80 to 90 degrees Celsius for 12 hours. The lenses were vialed and steamsterilized using one, three, and five autoclave cycles. Samples wereevaluated for bonding and ink adhesion by finger rubbing after the one,three, and five autoclave cycles.

Summary of Results:

-   -   1. The bonding with control formulation was very poor. It rubbed        off using a finger rub test.    -   2. Bonding with the experimental formulations B and C was good        using a finger rub test.    -   3. Cracking in the digitally encoded image made with ink with        higher level HEMA was noticeably lower.

Formulations having polyfunctional aziridine Crosslinker such as Ionac®PFAZ®-322 (Sybron Chemicals, Inc., Birmingham, N.J.) with 40% BX-HEMALLT reduce cracking in the digitally encoded image made with ink andimproved ink adhesion to a HEMA lens compared to TD-70A ink alone.Effective mechanical bonding is achievable with polyfunctional aziridinecrosslinker.

Example 6 Multifunctional Carbodiimide as a Crosslinker

This example provides improved adhesion of a pigmented dye to polymerlens by using multifunctional carbodiimides as bonding agent. Acrosslinked network is believed to be formed by such multifunctionalcarbodiimides (see, for example, Dow Chemical Company's productdescription of UCARLNK™ CROSSLINKERS for UCARLNK™XL-29SE Crosslinker,which is incorporated by reference herein). The carbodiimide is believedto cause a reaction between carboxylic acid groups contained in the lenspolymer and either a hydroxyl end group or amine end group contained inthe dye preparation (see, for example, March, Advanced OrganicChemistry, Second Edition, McGraw-Hill Book Company, New York, inparticular pages 363 through 365). Such a crosslinked network isbelieved to enable entrapment of dyes such as pigmented dye.

An example of a multifunctional carbodiimide usable with the presentinvention is UCARLNK™ XL-29SE (Dow Chemical Co., Midland, Mich.). Inaddition low viscosity of UCARLNK™ XL-29SE may provide added benefitwhen utilizing the ink with an inkjet printer. About 1 to 10 percent byweight UCARLNK™ XL-29SE may be reacted with a carboxylatedhydroxyethylmethyl acrylate polymer. The reaction may take place below,at, or above room temperature however elevated temperatures reducereaction time. The range of temperature may be room temperature to 900°C.

The purpose of this example is to evaluate the bonding of ink to apolymer using UCARLNK™ XL-29SE as a crosslinker and establishes thestabilization of the location of a pigmented dye in a polymer.

Reagents

Various formulations used in these examples are described herein.

Experiment

Control Formulation A:

1. TD-70A Cyan ink

Experimental Formulation B:

1. TD-70A Cyan ink

2. UCARLNK® XL-29SE (Dow Chemicals, Midland, Mich.) 2%

Experimental Formulation C:

1. TD-70A Cyan ink

2 UCARLNK™ XL-29SE (Dow Chemicals, Midland, Mich.) 2%

3. HEMA formulation BX-HEMA LLT 40%

Each formulation was mixed and ink jet printed on HEMA lenses using aBudjet IV printer (Fas-co Encoder, Chandler, Ariz.). In addition,thermal initiators and/or UV initiators of po lymerization arecontemplated for these formulations to improve adhesion and/or time forpolymerization. Digitally encoded images of letters were ink jet printedonto the HEMA lenses. The lenses were cured at 70 degrees Celsius for 16hours. The lenses were then hydrated and extracted in distilled water at80 to 90 degrees Celsius for 12 hours. The lenses were vialed and steamsterilized using one, three, and five autoclave cycles. Samples wereevaluated for bonding and ink adhesion by finger rubbing after the one,three, and five autoclave cycles.

Summary of Results:

-   -   1. The bonding with control formulation A was very poor. It        rubbed off using a finger rub test.    -   2. Bonding with the experimental formulations B and C was good        using a finger rub test.    -   3. Cracking in the digitally encoded images made with ink with        higher level HEMA was noticeably lower.

These results showed that formulations having a multifunctionalcarbodiimide crosslinkers such as UCARLNK™ XL29SE (Dow Chemicals,Midland, Mich.) with 40% BX-HEMA LL T reduce cracking and improved inkadhesion to a HEMA lens compared to TD-70 ink alone. Effectivemechanical bonding is achievable with multifunctional carbodiimidecrosslinkers such as UCARLNK™ XL29SE.

Example 7 Titanates and Zirconates as Crosslinkers

In addition to the polyfunctional aziridines and multifunctionalcarbodiimides discussed in the previous examples, a variety of otherbonding agents can also be used in the present invention. Alternativesinclude, organic titanates and zirconates, such as those distributed bySynetix and DuPont. These organic titanates and zirconates can promotethe adhesion of ink of digitized images to polymer surface. Preferredexamples are the TYZOR→series of DuPont Chemicals (see for exampleDuPont Tyzor→Organic Titanates publications, (General Brochure (2001)),(Product Selection Guide—USA (2001)), (Product List—USA (2001)),(Technical Note—Grade Chart (2001)), (Technical Note—Grade SelectionChart (2001)), (Technical Note—Printing Ink Additive (2001)), and(Technical Note—FDA—Food Contact (2001))) and the VERTEC™ series (suchas VERTEC™ IA10) of Synetix and ICI Chemical (see, for examplewww.synetix.com and Material Safety Data Sheets for these products).

For application to the present invention, these compounds may be usedalone or in combination with other bonding agents, includingcross-linkers, such as polyfunctional aziridines and multifunctionalcarbodiimides, to improve adhesion. Organic titanates are believed tocrosslink ink resin and polymer through reaction with active hydrogen ofhydroxyl or carboxyl groups in lens polymers with ink resin. As a resultof such cross-linking, adhesion of ink to polymer is improved, as wellas heat stability and water or solvent resistance. There are a number ofpreferred organic titanates commercially available, for example VERTEC™IA10, VERTEC™ PA12, TYZOR→AA-75, TYZOR→TBT, TYZOR→TPT and TYZOR→BPT.

Generally, organic titanates and zirconates can be used in the finishedink at a concentration between about 1% and about 20%, preferablybetween about 3% and about 10%, of weight of finished ink. Reactionspeed may increase with temperature.

Reagents

Typical inks that can include organic titanates as a cross-linkerinclude:

Reagent % by weight A. TD-70A 40–80 B. BX-HEMA LLT  5–70 C. VERTEC IA10 1–10 D. Thermal or UV initiator 0.1–3   A. TD-70A is described herein.This reagent should be anhydrous because organic titanates hydrolyzewhich cause inks to gel. B. BX-HEMA LLT C. VERTEC IA10 from Syntix,Oakbrook Terrace, IL D. Thermal initiator such as benzoyl peroxide(Sigma, St. Louis MO or Aldrich, Milwaukee, WI) or UV initiator such asIrgacure 184 from Ciba Geigy, Basel, Switzerland.Experimental

Inks including organic titanates, zirconates or both are mixed and inkjet printed on HEMA lens using an appropriate printer such as the BudjetIV printer (Fas-co Encoder, Chandler, Ariz.). The lenses are cured foran appropriate period of time. The lenses are then hydrated andextracted in distilled water at an appropriate temperature for anappropriate time. The lenses are vialed and steam sterilized using one,three, and five autoclave cycles. Samples are evaluated for bonding andink adhesion by finger rubbing after the one, three, and five autoclavecycles.

Example 8 Ink Jet Printing of Digitally Encoded Images on Lenses UsingReactive Dyes

Reagents

Various formulations used in these examples are described herein.

TD 103A: White pigmented printing ink Material Percent TD 103 46.7BX-HEMA LL T 46.7 IONAC PFAZ 322 4.7 Benzoyl Peroxide 1.9 Total 100TD103: White solvent based pigment ink Material Percent Range Whitedispersion X6985–185 43.8 30–50 30% Epon 2004 in EB Acetate 35.4 25–45PM acetate 9.4  5–15 Suresol 150ND 10.4  5–15 BYK UV 3500 1.0 0.5–2  Total 100 Viscosity = 8.6 cps, UL, 60 rpm, 25° C. Surface tension = 26dyne/cm (A detailed formulation for White dispersion 6985–185 is givenherein such as in Example 5) TD46: Red (Magenta) Reactive dye inkMaterials Percent Range DI water 71.47 60–80 Glycerin 6.67  1–201,3-propandiol 6.67  1–20 Reactive Red .180 13.33 10–20 Surfynol CT 1210.53 0.2–2.0 Triethyl Amine 10% in water 1.33 1–5 Total 100 Viscosity =3.5 centipoise, UL, 60 rpm, 25° C. Surface tension = 32 dynes/cm; pH =8.4. The ink was filtered through 0.45 micron Nylon filter membrane.Water = Main vehicle, carrier Glycerin, 1,3-propandiol = co-solventsSurfynol CT121 and 10% TEA solution = additive TD47: Yellow Reactive dyeink Materials Percent Range DI water 69 60–80 Glycerin 10  5–201,3-propandiol 10  5–20 Reactive Yellow 15 10  5–20 Surfynol CT-121 0.80.2–2.0 10% TEA solution 0.2 0.1–1.0 (5 drops) Total 100 Viscosity = 3.5centipoise, UL, 60 rpm, 25° C.; Surface tension = 32 dynes/cm; pH = 7.5The ink was filtered through 0.45 micron Nylon membrane Water = mainvehicle, main carrier Glycerin and 1,3-propandiol = co-solvent SurfynolCT 121 and TEA solution = additive TD92: Black Reactive dye inkMaterials Percent Range DI water 62.8 50–70 Versene 100XL 1 0.5–2.02-pyrolidone 8  5–20 Ethylene Glycol 8  5–20 Glycerin 10  5–20 ReactiveBlack 5 10  5–20 Surfynol 2502 0.2 0.1–1.0 Total 100 Viscosity = 3.1centipoise, UL, 60 rpm, 25° C.; Surface tension = 31.5 dynes/cm; pH =6.8 Water = main carrier Ethylene Glycol, Glycerin, 2-pyrolidone =Co-solvents Versene 100XL, Surfynol 252 = additive TD 106: FormulaTD-106: Blue reactive dye ink Material Percent Range DI water 17.8 10–25Versene 100XL 1.0 0.5–2.0 NMMNO 7  3–10 PEG 200 3  1–5 PEG 400 2  1–5PEG 600 2  1–5 Glycerin 3.5  1–10 Giv-Gard DXN 0.4 0.1–1.0 Surfynol 5040.1 0.05–0.5  Surfynol 465 0.2 0.05–0.5  Papicel Blue IJ-PG dye solution63 50–80 Total 100 Viscosity = 3.01 cps, UL, 60 rpm, 25° C. Surfacetension = 27.5 dynes/cm pH = 6.5 Versene 100 XL is a chelating agentfrom DOW chemical, San Carlos, CA Giv Gard DXN is a biocide from ANGUSCHEMICAL COMPANY, Buffalo Grove, IL NMMNO is 4-methylmorpholine N-Oxide97% from ALDRICH CHEMICAL, WI PEG 200, PEG 400, PEG 600 are PolyethyleneGlycols from DOW chemical, San Carlos, CA Surfynol 504, Surfynol 465 aresurfactants from Air Product from Allentown, PA Papicel Blue IJ-PG dyesolution from Eastwell Company in KoreaExperiment

A digital image of an annular ring about the size of the iris of a humaneye was created in Photoshop 6.0 program and stored on the computer of apiezo (Ultramark) 2000, Inkjet printer (Fas-Co Coders, Chandler, Ariz.).TD103, a titanium dioxide based, solvent based ink, was mixed withmonomer mix BX-HEMA LLT, crosslinker aziridine and thermal initiatorbenzoyl peroxide per formulation TD103A. The digital image of theannular ring was then inkjet printed on lenses and the lens with imagewas cured for 16 hours at 70 C.

A digital image of an annular circle about the size of the iris of ahuman eye was divided into four quadrants colored cyan, yellow, magentaand black was created in Photoshop 6.0. TD46, TD47, TD92 and TD106reactive dye based inks were placed in the ink cartridge of a modifiedHP550C thermal inkjet printer. The printer was modified to allow acontact lens to pass under the printhead by raising the printhead adistance sufficient to allow the curvature of the contact lens to not bein direct contact with the printhead while maintaining printing quality.The digital image was printed on both titanium dioxide printed andclear, unprinted lenses on the modified HP550C printer. The lenses wereexposed to a hot steam environment at 110 C for 30 minutes in anautoclave. After steaming, the lenses were hydrated and extracted in0.3% sodium carbonate saline of pH 11.1 at 50 to 60 C and evaluated forcolor intensity. The lenses were then vialed, packaged in salinesolution and autoclaved. Lenses were evaluated for mechanical bonding byfinger rubbing after one and three sterilization cycle.

Results:

-   -   1. All samples had well defined deep colors before hydration    -   2. After hydration, as determined by finger rub test;        -   All lenses remained opaque        -   Magenta and Cyan color were little lighter, possibly due to        -   expansion/swelling of lens polymer        -   Yellow and black color faded.    -   3. After sterilization, some samples exhibited reduced bonding        of opaque material and colors to lenses as determined by a        finger-rub test.

Example 9 Use of an Image Receiver Layer on a Contact Lens

The following example describes the use of an image receiver layerapplied to a polymer substrate, such as a contact lens, to improve theresolution and definition of an image printed on the polymer substrate.

ViviPrint™ 121

The contact lens was a (dry) hydrogel contact lens that was cast moldedfrom polymerizable hydrophilic monomers (2-hydroxyethylmethacrylate andmethacrylic acid), a crosslinking agent, and an initiator. During theprocesses of applying an image receiver layer, printing an image, andfixation, the dry hydrogel contact lens remained on the mold on which itwas formed.

The image receiver layer was composed of a 10% solution in industrialmethylated spirits (IMS) or 3A alcohol of ViviPrint™ 121, which is aneutralized poly(vinylpyrrolidone/dimethylaminopropylmethacrylamide)copolymer, CAS number 175893-71-1, supplied as a 10% in watercomposition with a viscosity of between about 7 to about 23 centipoisesat about 25 degrees Celsius, a nominal molecular weight of about1.05×10⁶ grams per mole, and a glass transition temperature (Tg) ofabout 184 degrees Celsius) (lot number 0M00054427, product ID 72417D,International Specialty Products, 1361 Alps Road, Wayne, N.J. 07470).The solution of 10% ViviPrint™ 121 in IMS had a viscosity of about 5.18centipoises and a surface tension of about 25.5 dynes per centimeter.Three drops of this solution was applied by pipette to a dry hydrogel(hydroxyethylmethacrylate) lens that had been previously treated withbase, and allowed to air-dry. The digital image file to be printed wasopened in a suitable graphics package (such as Paintshop Pro or AdobePhotoshop) on a personal computer and the digital image was printed,using inks containing reactive dyes, onto the image receiverlayer-coated lens by a desktop inkjet printer, such as a Lexmark 45SEink jet printer modified to print onto a lens. Any desktop inkjetprinter (for example, those manufactured by Hewlett Packard, Lexmark,and Canon), when modified to print onto a lens may be used. A desktopinkjet printer can be modified to print onto a lens by use of thecarriage containing the print heads and the rail on which the carriageis mounted, and of a separate, independent linear slide system totransport the lens in a manner. The carriage and transport systems areindependent. The throw distance from the print head to the lens is setby the height at which the carriage is mounted over the transport, andcan be adjusted to the desired distance. The range of the throw distancecan be from between about 0.1 mm to about 3.0 mm, or from between about0.25 to about 2.0 mm. Preferably the throw distance is between about 0.5mm to about 1.5 mm.

After the image was printed on the lens, the lens was subjected to afixation process wherein the lens was placed on a tripod inside a glassjar, which was in a laboratory oven that had been pre-heated to about100 to about 110 degrees Celsius. A sufficient amount of water was alsoin the jar such that when the jar was sealed there was heat and steampresent during the 60-minute fixation period. After the fixationprocess, the lens was hydrated and sterilized as follows: the lens wasremoved from its mold and hydrated in a 0.5% sodium bicarbonate solutionat about 60 degrees Celsius for between about 30 to about 40 minutes;the lens was then removed from the hydration solution, placed in a 0.9%sodium chloride solution, and sterilized in a pressure cooker orautoclave for about 25 minutes at between about 127 to about 132 degreesCelsius.

Following printing, fixation, hydration, and sterilization, the imagequality was visually assessed by observing inter-color bleed (the degreeof mixing between two colors printed next to each other), dot roundnessand spread, and the overall aesthetic appeal of the printed image. Thismethod gave a better quality than that obtained with the PVP K30treatment but required a two-step process (separate application of thebase treatment and the image receiver layer).

PVP K30

The contact lens was a (dry) hydrogel contact lens that was cast moldedfrom polymerizable hydrophilic monomers (2-hydroxyethylmethacrylate andmethacrylic acid), a crosslinking agent, and an initiator. During theprocesses of applying an image receiver layer, printing an image, andfixation, the dry hydrogel contact lens remained on the mold on which itwas formed.

The image receiver layer was composed of a 5% solution in a 5% sodiumphosphate aqueous solution of PVP K30, which is polyvinylpyrrolidonesupplied as a hygroscopic, amorphous white powder with a viscosity (fora 5% solution) of 3 centipoises at 25 degrees Celsius, a nominalmolecular weight of 60×10³ grams per mole, and a glass transitiontemperature (Tg) of 163 degrees Celsius (lot number G80920A, cataloguenumber 23,425-7, Sigma-Aldrich, Milwaukee, Wis.). This compositionallowed the simultaneous application of the image receiver layer and thebase treatment as a single solution. The dry hydrogel(hydroxyethylmethacrylate) lens was immersed in this solution for up to30 minutes, removed, the excess solution removed by wicking with anabsorbent material in contact with an edge of the lens, and allowed toair-dry. The digital image file to be printed was opened in a suitablegraphics package (such as Paintshop Pro or Adobe Photoshop) on apersonal computer and the digital image was printed, using inkscontaining reactive dyes, onto the image receiver layer-coated lens by adesktop inkjet printer, such as a Lexmark 45SE ink jet printer modifiedto print onto a lens. Any desktop inkjet printer (for example, thosemanufactured by Hewlett Packard, Lexmark, and Canon), when modified toprint onto a lens may be used. After the image was printed on the lens,the lens was subjected to a fixation process wherein the lens was placedon a tripod inside a glass jar, which was in a laboratory oven that hadbeen pre-heated to about 100 to about 110 degrees Celsius. A sufficientamount of water was also in the jar such that when the jar was sealedthere was heat and steam present during the 60-minute fixation period.After the fixation process, the lens was hydrated and sterilized asfollows: the lens was removed from its mold and hydrated in a 0.5%sodium bicarbonate solution at 60 degrees Celsius for 30 to 40 minutes;the lens was then removed from the hydration solution, placed in a 0.9%sodium chloride solution, and sterilized in a pressure cooker orautoclave for 25 minutes at 127 to 132 degrees Celsius.

Following printing, fixation, hydration, and sterilization, the imagequality was visually assessed by observing inter-color bleed (the degreeof mixing between two colors printed next to each other), dot roundnessand spread, and the overall aesthetic appeal of the printed image. Thismethod gave a slightly lower quality image in comparison to thatobtained by the ViviPrint™ 121 treatment described above in thisexample, but had the advantage of requiring only a single step to applyboth the base treatment and the image receiver layer.

Example 10 Use of an Image Receiver Layer on a Prior Layer on a ContactLens

The following example describes the use of an image receiver layerapplied to a prior polymer layer on a polymer substrate, such as acontact lens, to improve the resolution and definition of an imageprinted on the prior polymer layer. The polymer substrate was a HEMAhydrogel contact lens, and the prior polymer layer contained an opaquepigment.

Application of a prior polymer layer: The contact lens was a (dry)hydrogel contact lens that was cast molded from polymerizablehydrophilic monomers (2-hydroxyethylmethacrylate and methacrylic acid),a crosslinking agent, and an initiator. During the processes of applyinga prior polymer layer, base treatment, applying an image receiver layer,and printing an image, the dry hydrogel contact lens remained on themold on which it was formed.

A first polymer layer, containing the coloring agent titanium dioxide,was applied to the contact lens. This was achieved by ink jet printingusing a white-pigmented ink, containing titanium dioxide in apolymerizable hydrophilic monomer formulation that had a viscositysuitable to ink jet printing and that had physical properties (such asflexibility and linear expandability) compatible with the lens material.Preferred polymerizable hydrophilic monomers include, but are notlimited to, glyceryl methacrylate, N-N-dimethylacrylamide, andN-vinyl-2-pyrrolidinone.

A single print pass at a print resolution of 1085 dots per inch (downweb) by 185 dots per inch (cross web) was made with a piezo ink jetprinting head (Xaar XJ 128/200 dpi) to produce a ring-shaped image,white-pigmented polymer layer on the contact lens. The ring-shaped imagehad good wetting and opacity. The printed white-pigmented ink was curedusing ten cycles through a Fusion ultraviolet light system with 500 WH-bulbs, at a speed of 10 meters per minute, to produce cured, generallytack-free lenses. The resulting cured, white-pigmented polymer layerserved as a prior polymer layer onto which the image receiver layer andCYMK (that is to say, a Cyan, Yellow, Magenta, Black four-color process)ink image were later applied.

Base treatment: The lens was soaked in a 10% sodium phosphate solutionat 60 degrees Celsius for 30 minutes, avoiding full hydration ordistortion. After removal from the base solution, excess fluid wasremoved from the lens with a lint-free cloth, with care taken to avoiddirect contact of the cloth to the lens. The lens was air-dried for 5minutes.

Image receiving layer: Two to three drops of a 10% solution inindustrial methylated spirits (IMS) of ViviPrint™ 121 was pipetted ontothe lens to evenly coat the lens surface, with the excess solutionallowed to flow off the lens onto the mold. Ethanol or denatured ethanol(for example, 3A alcohol) may be used as an alternative solvent. Thelens was air-dried until the alcohol had evaporated, resulting in a thinlayer of ViviPrint™ 121 on the lens, that appeared matte and felt dry tothe touch.

Reactive dye printing: Aqueous inks containing reactive dyes were usedin a CYMK four-color printing process. The reactive dyes includedFDA-approved Reactive Red 180, Reactive Blue 21, Reactive Yellow 15, andReactive Black 5. Examples of ink formulations are given in TABLE 1.

TABLE 1 INK COLOR BIR 1 BIR 11 BIR 2 BIR 12 C Y M K MATERIALS (Cyan)(Yellow) (Magenta) (Black) Reactive Blue 21 (23%)   44%   0%    0%   0%Reactive Red 180 (25%)   0%   0% 66.67%   0% Reactive Yellow 15 (10%)  0%   50%    0%   0% Reactive Black 5 (25%)   0%   0%    0%   10%N-methylmorpholine N-oxide   0% 18.7%    0%   0% 2-pyrrolidinone   6%  2%    6%   6% De-ionized water 29.2% 18.7%  8.48% 66.5% Ethyleneglycol   0%   10%    0%   0% Glycerol   10%   0%    8%   8%Polyethyleneglycol (PEG 200)   10%   0%   10%   9% Versene 100XL (Dow) 0.4%  0.4%  0.4%  0.4% Proxel GXL (Avecia)  0.3%  0.1%  0.3%  0.1%Dynol 604 (Air Products)  0.1%  0.1%  0.15%   0% Filtration 1.0 micron1.0 micron 1.0 micron 1.0 micron Viscosity at 25 degrees Celsius 3.003.33 3.08 3.03 (centipoises) Original pH 6.45 7.38 6.71 6.4 Adjusted pH— 6.49 — — Surface tension (dynes per centimeter) 28.0 31.0 30.5 38.2

The mold bearing the attached contact lens was fed through an ink jetprinter (model Lexmark 45se). The digital image file to be printed wasopened in a suitable graphics package (such as Paintshop Pro or AdobePhotoshop) on a personal computer and the digital image was printed,using inks containing reactive dyes, onto the image receiverlayer-coated lens by a desktop inkjet printer, such as a Lexmark 45SEink jet printer modified to print onto a lens. Any desktop inkjetprinter (for example, those manufactured by Hewlett Packard, Lexmark,and Canon), when modified to print onto a lens may be used. A desktopinkjet printer can be modified to print onto a lens by use of thecarriage containing the print heads and the rail on which the carriageis mounted, and of a separate, independent linear slide system totransport the lens in a manner. The carriage and transport systems areindependent. The throw distance from the print head to the lens is setby the height at which the carriage is mounted over the transport, andcan be adjusted to the desired distance. Print resolution was 600 dotsper inch (normal mode). After printing, the lens was air-dried for a fewminutes then subjected to post-printing processes (fixation, hydration,and sterilization).

Post-printing processes: After the image was printed on the lens, thelens was subjected to a fixation process wherein the lens was placed ona tripod inside a glass jar, which was in a laboratory oven that hadbeen pre-heated to about 100 to about 110 degrees Celsius. A sufficientamount of water was also in the jar such that when the jar was sealedthere was heat and steam present during the 60-minute fixation period.After the fixation process, the lens was hydrated and sterilized asfollows: the lens was removed from its mold and hydrated in a 0.5%sodium bicarbonate solution at 60 degrees Celsius for 30 to 40 minutes;the lens was then removed from the hydration solution, placed in a 0.9%sodium chloride solution, and sterilized in a pressure cooker orautoclave for 25 minutes at 127 to 132 degrees Celsius.

Following printing, fixation, hydration, and sterilization, the imagequality was visually assessed by observing color intensity, inter-colorbleed (the degree of mixing between two colors printed next to eachother), dot roundness and spread, and the overall aesthetic appeal ofthe printed image. This method gave a good quality image in comparisonto the desired level of image quality (for example, an inkjet imageprinted conventionally onto paper).

All publications, including patent documents and scientific articles,referred to in this application and the bibliography and attachments areincorporated by reference in their entirety for all purposes to the sameextent as if each individual publication were individually incorporatedby reference.

All headings are for the convenience of the reader and should not beused to limit the meaning of the text that follows the heading, unlessso specified.

What is claimed is:
 1. An article of manufacture, comprising: a) apolymer substrate, and b) a digitally encoded image made with ink;wherein said polymer substrate forms a lens; wherein said polymersubstrate is subjected to a pre-treatment process that precedes theapplication of said digitally encoded image to said polymer substrate;and wherein said pre-treatment process results in an enhanced imagequality of said digitally encoded image.
 2. The article of manufactureof claim 1, wherein said digitally encoded image is made at least inpart using said pre-treatment process.
 3. The article of manufacture ofclaim 1, wherein said pre-treatment process comprises one or morechemical modification of said polymer substrate.
 4. The article ofmanufacture of claim 3, wherein said one or more chemical modificationof said polymer substrate is selected from the group consisting of:chemical cleaning, chemical texture modification, chemical orelectrochemical activation or creation of reactive groups on or withinsaid polymer substrate, application of one or more chemicals to saidpolymer substrate, and combinations thereof.
 5. The article ofmanufacture of claim 1, wherein said pre-treatment process comprises theapplication of an image receiver layer.
 6. The article of manufacture ofclaim 5, wherein said image receiver layer comprises a chemical coatingapplied to the surface of said polymer substrate.
 7. The article ofmanufacture of claim 5, wherein said image receiver layer has athickness of between about 0.1 micrometers to about 200 micrometers. 8.The article of manufacture of claim 5, wherein said image receiver layerhas a thickness of between about 0.1 micrometers to about 100micrometers.
 9. The article of manufacture of claim 5, wherein saidimage receiver layer has a thickness of between about 0.1 micrometers toabout 20 micrometers.
 10. The article of manufacture of claim 5, whereinsaid image receiver layer is applied to the entire area of said polymersubstrate.
 11. The article of manufacture of claim 5, wherein said imagereceiver layer is applied to one or more partial area of said polymersubstrate.
 12. The article of manufacture of claim 5, wherein said imagereceiver layer is applied to a prior layer on or in said polymersubstrate.
 13. The article of manufacture of claim 12, wherein saidprior layer is a prior polymer layer containing a coloring agent. 14.The article of manufacture of claim 5, wherein said image receiver layercomprises a highly absorbent polymer.
 15. The article of manufacture ofclaim 14, wherein said highly absorbent polymer comprises apolyvinylpyrrolidone homopolymer, a polyvinylpyrrolidone copolymer, apolyacrylamide homopolymer, a polyacrylamide copolymer, a polyacrylatehomopolymer, a polyacrylate copolymer, a proteinaceous material, acarbohydrate, or a combination thereof.
 16. The article of manufactureof claim 5, wherein said image receiver layer is non-transientlyincorporated into or onto said polymer substrate.
 17. The article ofmanufacture of claim 5, wherein said image receiver layer is a temporarycoating.
 18. The article of manufacture of claim 17, wherein said imagereceiver layer is substantially removable during the normalpost-fixation processes.
 19. The article of manufacture of claim 5,wherein said image receiver layer is applied prior to, simultaneouslywith, or after exposure of said polymer substrate to an activatingsubstance.
 20. The article of manufacture of claim 5, wherein said imagereceiver layer is compatible with a base treatment of said polymersubstrate.
 21. The article of manufacture of claim 19, wherein saidactivating substance comprises a base.
 22. The article of manufacture ofclaim 5, wherein said image receiver layer is applied by direct coating,application of droplets or microdroplets, ink jet printing, soaking,impregnation, spin coating, dip coating, curtain coating, or padprinting.
 23. A method of making an article of manufacture comprising apolymer substrate and a digitally encoded image made with ink, whereinsaid polymer substrate forms a lens, comprising: a) subjecting saidpolymer substrate to a pre-treatment process; and b) applying saiddigitally encoded image to said polymer substrate, wherein saidpre-treatment process results in an enhanced image quality of saiddigitally encoded image.
 24. The method of claim 23, wherein saidpre-treatment process is applied to said lens.
 25. The method of claim23, wherein said digitally encoded image is applied to said lens. 26.The method of claim 25, wherein said digitally encoded image is appliedin whole or in part directly to said lens.
 27. The method of claim 25,wherein said digitally encoded image is applied in whole or in partindirectly to said lens.
 28. The method of claim 25, wherein saiddigitally encoded image is applied to one or more portions of said lens.29. The method of claim 23, wherein said digitally encoded image is madeat least in part using said pre-treatment process.
 30. The method ofclaim 23, wherein said pre-treatment process is applied to one or moreportions of the polymer substrate.
 31. The method of claim 23 whereinsaid pre-treatment process comprises one or more chemical modificationof said polymer substrate.
 32. The method of claim 31, wherein said oneor more chemical modification of said polymer substrate is selected fromthe group consisting of: chemical cleaning, chemical texturemodification, chemical or electrochemical activation or creation ofreactive groups on or within said polymer substrate, application of oneor more chemicals to said polymer substrate, and combinations thereof.33. The method of claim 23, wherein said pre-treatment process comprisesthe application of an image receiver layer.
 34. The method of claim 33,wherein said image receiver layer comprises a chemical coating appliedto the surface of said polymer substrate.
 35. The method of claim 33,wherein said image receiver layer has a thickness of between about 0.1micrometers to about 200 micrometers.
 36. The method of claim 33,wherein said image receiver layer has a thickness of between about 0.1micrometers to about 100 micrometers.
 37. The method of claim 33,wherein said image receiver layer has a thickness of between about 0.1micrometers to about 20 micrometers.
 38. The method of claim 33, whereinsaid image receiver layer is applied to the entire area of said polymersubstrate.
 39. The method of claim 33, wherein said image receiver layeris applied to one or more partial area of said polymer substrate. 40.The method of claim 33, wherein said image receiver layer is applied toa prior layer on or in said polymer substrate.
 41. The method of claim40, wherein said prior layer is a prior polymer layer containing acoloring agent.
 42. The method of claim 33, wherein said image receiverlayer comprises a highly absorbent polymer.
 43. The method of claim 42,wherein said highly absorbent polymer comprises a polyvinylpyrrolidonehomopolymer, a polyvinylpyrrolidone copolymer, a polyacrylamidehomopolymer, a polyacrylamide copolymer, a polyacrylate homopolymer, apolyacrylate copolymer, a proteinaceous material, a carbohydrate, or acombination thereof.
 44. The method of claim 33, wherein said imagereceiver layer is non-transiently incorporated into or onto said polymersubstrate.
 45. The method of claim 33, wherein said image receiver layeris a temporary coating.
 46. The method of claim 45, wherein said imagereceiver layer is substantially removable during the normalpost-fixation processes.
 47. The method of claim 33, wherein said imagereceiver layer is applied prior to, simultaneously with, or afterexposure of said polymer substrate to an activating substance.
 48. Themethod of claim 33, wherein said image receiver layer is compatible witha base treatment of said polymer substrate.
 49. The method of claim 47,wherein said activating substance comprises a base.
 50. The method ofclaim 33, wherein said image receiver layer is applied by directcoating, application of droplets or microdroplets, ink jet printing,soaking, impregnation, spin coating, dip coating, curtain coating, orpad printing.
 51. An article of manufacture, comprising: 2.) a polymersubstrate 3.) a digitally encoded image made with ink comprisingreactive components, wherein said polymer substrate forms a lens;wherein said digitally encoded image is applied to said polymersubstrate by ink jet printing; and wherein each said reactive componentis stored in an ink jet printer cartridge.
 52. The article ofmanufacture of claim 51, wherein said reactive components are stored inseparate ink jet printer cartridges.
 53. The article of manufacture ofclaim 51, wherein said ink comprises one or more polymerizable monomerand one or more initiator; and wherein each said one or morepolymerizable monomer and said one or more initiator are stored in anink jet printer cartridge.
 54. The article of manufacture of claim 51,wherein said reactive components are stored in separate ink jet printercartridges.